Water- and oil-repellent, antistatic composition

ABSTRACT

A water- and oil-repellent, antistatic composition comprises (a) at least one nonpolymeric ionic salt consisting of (i) at least one cation selected from the group consisting of monovalent metal cations, divalent metal cations, and organic onium cations, and (ii) at least one weakly coordinating anion, the conjugate acid of the anion having an acidity greater than or equal to that of a hydrocarbon sulfonic acid, and with the proviso that the anion is organic or fluoroorganic when the cation is a metal; (b) at least one fluorochemical repellency-imparting additive or repellent; and (c) at least one insulating material. The composition exhibits good antistatic and repellency characteristics.

This application is a divisional of U.S. Ser. No. 10/458,971, filed Jun.11, 2003, now U.S. Pat. No. 6,784,237, which is a divisional of U.S.Ser. No. 09/474,711, filed Dec. 29, 1999, now U.S. Pat. No. 6,592,988,the disclosures of which are herein incorporated by reference.

FIELD OF THE INVENTION

This invention relates to compositions that exhibit both repellency andantistatic characteristics. This invention further relates to fibers,films, fabrics, coatings, and molded or blown articles comprising thecompositions. In other aspects, this invention also relates to a topicaltreatment composition and to processes for imparting both repellency andantistatic characteristics to substrates.

BACKGROUND OF THE INVENTION

Various fluorochemicals have been used to impart water and oilrepellency, as well as soil resistance, to a variety of substrates (forexample, textiles, carpet, leather, paper, and non-woven webs). Thesefluorochemicals have most often been applied topically (for example, byspraying, padding, or finish bath immersion), but some fluorochemicalshave also been useful as polymer melt additives for preparing water- andoil-repellent polymeric fibers, films, fabrics, etc. The resultingrepellent substrates have found use in numerous applications where waterand/or oil repellency (as well as soil resistance) characteristics havebeen valued.

For some applications, however, antistatic properties have also beennecessary or desirable.

Electrostatic charge buildup is responsible for a variety of problems inthe processing and use of many industrial products and materials.Electrostatic charging can cause materials to stick together or to repelone another. This is a particular problem in fiber and textileprocessing. In addition, static charge buildup can cause objects toattract dirt and dust, thereby decreasing the effectiveness offluorochemical repellents.

Sudden electrostatic discharges from insulating objects can also be aserious problem. With photographic film, such discharges can causefogging and the appearance of artifacts. When flammable materials arepresent (for example, in a surgical environment), a static electricdischarge can serve as an ignition source, resulting in fires and/orexplosions. Static is a particular problem in the electronics industry,since modem electronic devices are extremely susceptible to permanentdamage by static electric discharges.

However, conventional antistats (many of which are humectants that relyon the adsorption and conductivity of water for charge dissipation) havegenerally not been very effective in combination with fluorochemicalrepellents. The result of such combination has often been a substantialdeterioration (or even elimination) of either antistatic or repellencycharacteristics (or both), relative to the use of either additive alone.

Furthermore, it has been particularly difficult to combine conventionalantistats and fluorochemical repellents in polymer melt processingapplications, as, for example, the water associated with humectantantistats vaporizes rapidly at melt processing temperatures. This hasresulted in the undesirable formation of bubbles in the polymer and hascaused screw slippage in extrusion equipment. Many antistats have alsolacked the requisite thermal stability, leading to the production ofobjectionable odors (for example, in melt blowing applications, wherehigh extrusion temperatures are involved).

Thus, there remains a need in the art for antistatic agents andrepellents that can be effectively combined to impart both goodantistatic characteristics and good repellency characteristics tosubstrates and that, in particular, can be utilized as melt additiveswithout causing processing problems or melt defects.

SUMMARY OF THE INVENTION

Briefly, in one aspect, this invention provides a water- andoil-repellent, antistatic composition comprising (a) at least onenonpolymeric ionic salt consisting of (i) at least one monovalent metalcation, divalent metal cation, or organic onium cation (for example, aquaternary ammonium ion) and (ii) at least one weakly coordinatinganion, the conjugate acid of the anion having an acidity greater than orequal to that of a hydrocarbon sulfonic acid (for example, abis(perfluoroalkanesulfonyl)imide ion), and with the proviso that theanion is organic or fluoroorganic when the cation is a metal; (b) atleast one fluorochemical repellency-imparting additive or repellent; and(c) at least one insulating material. As used herein, the term “organiconium cation” means a positively charged organic ion having at leastpart of its charge localized on at least one heteroatom (for example,nitrogen, phosphorus, sulfur, iodine, or oxygen). Preferably, theinsulating material is a thermoplastic or thermosetting polymer (morepreferably, thermoplastic), and the composition is prepared by forming ablend (more preferably, a melt blend) of the components.

It has been discovered that the above-described class of ionic saltantistatic agents or antistats can be effectively combined withfluorochemical repellents to impart both good antistatic characteristicsand good repellency characteristics to a variety of insulatingmaterials. The antistats and repellents can be combined not only intopical treatments (external additives) but even (and preferably) asmelt additives (internal additives) without causing processing problemsor melt defects. The antistat/repellent combination used in thecomposition of the invention is surprisingly effective at dissipatingthe static charge that can accumulate in an otherwise insulatingsubstrate such as a polymer film or fabric, while also imparting durablewater and oil repellency (and soil resistance). Even more suprisingly,when used in topical treatments or as polymer melt additives inpolypropylene melt-blown nonwoven fabric, certain preferred antistatsexhibit synergistic behavior when combined with the repellent(s), inthat better static dissipation rates are obtained than when theantistats are used alone.

The combination of ionic salt antistat(s) and fluorochemicalrepellent(s) used in the composition of the invention is compatible witha variety of polymers. Since many of the antistats are hydrophobic(immiscible with water), the antistatic performance of the combinationis often relatively independent of atmospheric humidity levels anddurable even under exposure to aqueous environments. In addition, sincemany of the antistats are stable at temperatures up to 300-500° C., thecombination of such antistat(s) with thermally stable fluorochemicalrepellent(s) is particularly well-suited for use in high temperaturepolymer melt additive applications and in applications where the usetemperatures are very high.

The combination of ionic salt antistat(s) and fluorochemicalrepellent(s) used in the composition of the invention therefore meetsthe need in the art for antistatic agents and repellents that can beeffectively combined to impart both good antistatic characteristics andgood repellency characteristics to substrates and that, in particular,can be utilized as melt additives without causing processing problems ormelt defects.

In other aspects, this invention also provides fiber, fabric, film, acoating, and a molded or blown article comprising the composition of theinvention; processes for imparting both repellency and antistaticcharacteristics to a substrate, for example, by bulk addition or bytopical treatment; and a topical treatment composition comprising (a) atleast one nonpolymeric ionic salt consisting of (i) at least onemonovalent metal cation, divalent metal cation, or organic onium cationand (ii) at least one weakly coordinating anion, the conjugate acid ofthe anion having an acidity greater than or equal to that of ahydrocarbon sulfonic acid, and with the proviso that the anion isorganic or fluoroorganic when the cation is a metal, and (b) at leastone fluorochemical repellency-imparting additive or repellent.

DETAILED DESCRIPTION OF THE INVENTION

Antistats

Ionic salts suitable for use as antistats in the composition of theinvention are those that consist of a monovalent or divalent metalcation (preferably, monovalent) or an organic onium cation (preferably,an organic onium cation) and a weakly coordinating anion. Suitable metalcations include, for example, lithium, calcium, sodium, potassium,magnesium, zinc, iron, nickel, and copper, with sodium and lithium beingpreferred. The organic onium cation can comprise a heteroatom (forexample, nitrogen, phosphorus, sulfur, iodine, or oxygen; preferably,nitrogen or phosphorus; more preferably, nitrogen) as the charge centeror as a component element in a charge-delocalized chain or ringstructure. The organic onium cation can be cyclic (that is, where thecharge center(s) of the cation are ring atoms) or acyclic (that is,where the charge center(s) of the cation are not ring atoms but can havecyclic substituents). The cyclic cations can be aromatic, unsaturatedbut nonaromatic, or saturated, and the acyclic cations can be saturatedor unsaturated.

The cyclic cations can contain one or more ring heteroatoms (forexample, nitrogen, oxygen, or sulfur), and the ring atoms can bearsubstituents (for example, hydrogen, halogen, or organic groups such asalkyl, alicyclic, aryl, alkalicyclic, alkaryl, alicyclicalkyl, aralkyl,aralicyclic, and alicyclicaryl groups). Separate alkyl substituents canbe joined together to constitute a unitary alkylene radical of from 2 to4 carbon atoms forming a ring structure. Organic substituents cancontain one or more heteroatoms such as, for example, nitrogen, oxygen,sulfur, phosphorus, or halogen (and thus can be fluoroorganic innature).

The acyclic cations can have at least one (preferably, at least two;more preferably, at least three; most preferably, four) chargecenter-bonded organic substituents or R groups, with the remainingsubstituents being hydrogen. The R groups can be cyclic or acyclic,saturated or unsaturated, aromatic or nonaromatic, and can contain oneor more heteroatoms such as, for example, nitrogen, oxygen, sulfur,phosphorus, or halogen (and thus can be fluoroorganic in nature).

Preferably, the organic onium cation is acyclic or unsaturated cyclic.More preferably, it is acyclic or aromatic, most preferably, acyclic.

Preferred acyclic organic onium cations are nitrogen onium (ammonium)and phosphorus onium (phosphonium) cations that are quaternary ortertiary (most preferably, quaternary) cations. The quaternary andtertiary cations are preferably of low symmetry (having at least two,preferably at least three, different charge center-bonded organicsubstituents or R groups as defined above) and more preferably containat least one hydroxyl group in at least one charge center-bonded organicsubstituent. Most preferred acyclic organic onium cations are thenitrogen onium cations described below for the ionic salt antistats ofFormula I.

Preferred aromatic organic onium cations are the nitrogen onium cationsselected from the group consisting of

wherein R₁, R₂, R₃, R₄, R₅, and R₆ are independently selected from thegroup consisting of H, F, alkyl groups of from 1 to about 18 carbonatoms (preferably, from 1 to about 11 carbon atoms), two said alkylgroups joined together to form a unitary alkylene radical of from 2 to 4carbon atoms forming a ring structure, and phenyl groups; and whereinsaid alkyl groups, alkylene radicals, or phenyl groups can comprise oneor more substituent groups (preferably, a group that is capable ofhydrogen bonding, for example, an amino, hydroxyl, acetyl, or acetamidegroup, or an electron-withdrawing group, for example, F—, Cl—, CF₃—,SF₅—, CF₃S—, (CF₃)₂CHS—, and (CF₃)₃ CS—).

Preferred unsaturated cyclic, nonaromatic organic onium cations includethe nitrogen onium cations represented by the following formula

where R₁, R₂, R₃, R₄, R₅, R₆, and R₇ are defined as R₁, R₂, R₃, R₄, R₅,and R₆ are defined above for the preferred aromatic organic oniumcations.

Suitable weakly coordinating anions have a conjugate acid that is atleast as acidic as a hydrocarbon sulfonic acid (preferably, ahydrocarbon sulfonic acid having from 1 to about 20 carbon atoms; morepreferably, an alkane, aryl, or alkaryl sulfonic acid having from 1 toabout 8 carbon atoms; even more preferably, methane or p-toluenesulfonic acid; most preferably, p-toluene sulfonic acid). Preferably,the conjugate acid is a strong acid. More preferably, the Hammettacidity function, H₀, of the neat conjugate acid of the anion is lessthan about —7 (most preferably, less than about —10).

Representative examples of suitable weakly coordinating anions includeBF₄—; PF₆—; SbF₆—; AsF₆—; ClO₄—; NO₃—; Cl—; Br—; F—; HSO₄—; H₂PO₄—;organic anions such as alkane, aryl, and alkaryl sulfonates; fluorinatedand unfluorinated tetraarylborates; carboranes and halogen-, alkyl-, orhaloakyl-substituted carborane anions including metallocarborane anions;teflates (for example, —OTeF₅, —B(OTeF₅)₄, and —Pd(OTeF₅)₄); andfluoroorganic anions such as perfluoroalkanesulfonates,cyanoperfluoroalkanesulfonylamides,bis(cyano)perfluoroalkanesulfonylmethides,bis(perfluoroalkanesulfonyl)imides,bis(perfluoroalkanesulfonyl)methides, andtris(perfluoroalkanesulfonyl)methides; and the like. Preferred anionsinclude organic and fluoroorganic anions (more preferably, alkane, aryl,and alkaryl sulfonates, as well as perfluoroalkanesulfonates,bis(perfluoroalkanesulfonyl)imides, andtris(perfluoroalkanesulfonyl)methides; most preferably, alkanesulfonates, perfluoroalkanesulfonates, andbis(perfluoroalkanesulfonyl)imides).

The fluoroorganic anions can be either fully fluorinated, that isperfluorinated, or partially fluorinated (within the organic portionthereof). Preferred fluoroorganic anions include those that comprise atleast one highly fluorinated alkanesulfonyl group, that is, aperfluoroalkanesulfonyl group or a partially fluorinated alkanesulfonylgroup wherein all non-fluorine carbon-bonded substituents are bonded tocarbon atoms other than the carbon atom that is directly bonded to thesulfonyl group (preferably, all non-fluorine carbon-bonded substituentsare bonded to carbon atoms that are more than two carbon atoms away fromthe sulfonyl group).

Preferably, the fluoroorganic anion is at least about 80 percentfluorinated (that is, at least about 80 percent of the carbon-bondedsubstituents of the anion are fluorine atoms). More preferably, theanion is perfluorinated (that is, fully fluorinated, where all of thecarbon-bonded substituents are fluorine atoms). The anions, includingthe preferred perfluorinated anions, can contain one or more catenary(that is, in-chain) heteroatoms such as, for example, nitrogen, oxygen,or sulfur.

Preferred fluoroorganic anions include perfluoroalkanesulfonates,bis(perfluoroalkanesulfonyl)imides, andtris(perfluoroalkanesulfonyl)methides. The perfluoroalkanesulfonates andbis(perfluoroalkanesulfonyl)imides are more preferred anions, with theperfluoroalkanesulfonates being most preferred.

The ionic salt antistats can be solids or liquids under use conditionsbut preferably have melting points less than about 150° C. (morepreferably, less than about 50° C.; most preferably, less than about 25°C.). Liquid ionic salts are preferred due to their generally betterstatic dissipative performance. For use as polymer melt additives, theionic salt antistats are preferably stable at temperatures of about 250°C. and above (more preferably, about 300° C. and above) and arepreferably miscible with the insulating material at the melt processingtemperature. (In other words, the onset of decomposition of theantistats is above such temperatures.) Preferred ionic salt antistatsfor polymer melt additive applications include those having cationsselected from the group consisting of alkyl phosphonium cations,aromatic nitrogen onium cations (preferably, the preferred aromaticorganic onium cations set forth above), and acyclic nitrogen oniumcations (preferably, the cations shown in Formula I below); and havingorganic or fluoroorganic anions (preferably, anions selected from thegroup consisting of alkane sulfonates, aryl sulfonates, alkarylsulfonates, perfluoroalkanesulfonates,bis(perfluoroalkanesulfonyl)imides, andtris(perfluoroalkanesulfonyl)methides; more preferably, alkanesulfonates, perfluoroalkanesulfonates, andbis(perfluoroalkanesulfonyl)imides); most preferably,perfluoroalkanesulfonates and bis(perfluoroalkanesulfonyl)imides.

The antistats are also preferably hydrophobic. Thus, a preferred classof ionic salt antistats for use in the composition of the inventionincludes those that consist of (a) an aromatic nitrogen onium cationselected from the group consisting of

wherein R₁, R₂, R₃, R₄, R₅ and R₆ are independently selected from thegroup consisting of H, F, alkyl groups of from 1 to about 18 carbonatoms (preferably, from 1 to about 11 carbon atoms), two said alkylgroups joined together to form a unitary alkylene radical of from 2 to 4carbon atoms forming a ring structure, and phenyl groups; and whereinsaid alkyl groups, alkylene radicals, or phenyl groups can comprise oneor more substituent groups (preferably, an electron-withdrawing group,for example, F—, Cl—, CF₃—, SF₅—, CF₃S—, (CF₃)₂CHS—, and (CF₃)₃ CS—);and (b) a weakly coordinating fluoroorganic anion in accordance with theabove description or a weakly coordinating anion selected from the groupconsisting of BF₄—, PF₆—, AsF₆—, and SbF₆—. This preferred classcomprises a most preferred subclass of the hydrophobic ionic liquidsdescribed in U.S. Pat. No. 5,827,602 (Koch et al.), the description ofthe members of which is incorporated herein by reference.

Another preferred class of ionic salt antistats useful in preparing thecomposition of the invention is the class of compounds represented byFormula I below(R₁)_(4-z)N⁺[(CH₂)_(q)OR₂]_(z)X⁻  (I)wherein each R₁ is independently selected from the group consisting ofalkyl, alicyclic, aryl, alkalicyclic, alkaryl, alicyclicalkyl, aralkyl,aralicyclic, and alicyclicaryl moieties that can contain one or moreheteroatoms such as, for example, nitrogen, oxygen, sulfur, phosphorus,or halogen (and thus can be fluoroorganic in nature); each R₂ isindependently selected from the group consisting of hydrogen and themoieties described above for R₁; z is an integer of 1 to 4; q is aninteger of 1 to 4; and X is a weakly coordinating alkane sulfonate, arylsulfonate, alkaryl sulfonate, or fluoroorganic anion as described above(preferably, a fluoroorganic anion). R₁ is preferably alkyl, and R₂ ispreferably selected from the group consisting of hydrogen, alkyl, andacyl (more preferably, hydrogen or acyl; most preferably, hydrogen).Most preferably, z is 1, q is 2, R₁ is alkyl, and R₂ is hydrogen.

Many of the above-described ionic salt antistats (for example, metalbis(perfluoroalkanesulfonyl)imides, metal perfluoroalkanesulfonates,onium halides, onium alkanesulfonates, onium arylsulfonates, oniumtetrafluoroborates, and onium hexafluorophosphates) are commerciallyavailable and can also be prepared by standard methods known in the art.Other ionic salt antistats comprising an organic onium cation can beprepared by ion exchange or metathesis reactions, which are also wellknown in the art. For example, a precursor onium salt can be combinedwith a precursor metal salt or the corresponding acid of a weaklycoordinating anion in aqueous solution. Upon combining, the desiredproduct (the onium salt of the weakly coordinating anion) precipitates(as a liquid or solid) or can be preferentially extracted into anorganic solvent (for example, methylene chloride). The product can beisolated by filtration or by liquid/liquid phase separation, can bewashed with water to completely remove byproduct metal salt or acid (ifpresent), and can then be dried thoroughly under vacuum to remove allvolatiles (including water and organic solvent, if present). Similarmetathesis reactions can be conducted in organic solvents (for example,acetonitrile) rather than in water, and, in this case, the saltbyproduct generally preferentially precipitates, while the desiredproduct salt remains dissolved in the organic solvent (from which it canbe isolated using standard experimental techniques).

Weakly coordinating fluoroorganic anions (for use in preparing suchionic salts) can be prepared by standard methods known in the art, andmetal salts of many are commercially available. Such methods include theanion precursor preparative methods described in the followingreferences, the descriptions of which are incorporated herein byreference: imide precursors—U.S. Pat. No. 5,874,616 (Howells et al.),U.S. Pat. No. 5,723,664 (Sakaguchi et al.), U.S. Pat. No. 5,072,040(Armand), and U.S. Pat. No. 4,387,222 (Koshar); methide precursors—U.S.Pat. No. 5,554,664 (Lamanna et al.) and U.S. Pat. No. 5,273,840(Dominey); sulfonate precursors—U.S. Pat. No. 5,176,943 (Wou), U.S. Pat.No. 4,582,781 (Chen et al.), U.S. Pat. No. 3,476,753 (Hanson), and U.S.Pat. No. 2,732,398 (Brice et al.); sulfonate, imide, and methideprecursors having caternary oxygen or nitrogen in a fluorochemicalgroup—U.S. Pat. No. 5,514,493 (Waddell et al.); disulfone precursors—R.J. Koshar and R. A. Mitsch, J. Org. Chem., 38, 3358 (1973) and U.S. Pat.No. 5,136,097 (Armand).

In general, cyano-containing methides and amides containingfluoroalkanesulfonyl groups can be prepared by the reaction offluoroalkanesulfonyl fluorides, R_(f)SO₂F, with anhydrous malononitrileor cyanamide, respectively, in the presence of a non-nucleophilic base.This synthetic procedure is described in Scheme 1 of U.S. Pat. No.5,874,616 (Howells et al.) for the preparation ofbis(fluoroalkanesulfonyl)imides (the description of which isincorporated herein by reference) and involves the substitution ofeither malononitrile or cyanamide for the fluoroalkanesulfonamide. Theresulting intermediate non-nucleophilic base cation-containing methideor amide salt can be converted to the desired cation salt (typicallylithium) via standard metathesis reactions well known in the art.

Representative examples of useful ionic salt antistats includeoctyldimethyl-2-hydroxyethylammonium bis(trifluoromethylsulfonyl)imide:

-   [C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻N(SO₂CF₃)₂],    octyldimethyl-2-hydroxyethylammonium perfluorobutanesulfonate:-   [C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂C₄F₉],    octyldimethyl-2-hydroxyethylammonium trifluoromethanesulfonate:-   [C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CF₃],    octyldimethyl-2-hydroxyethylammonium    tris(trifluoromethanesulfonyl)methide:-   [C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻C(SO₂CF₃)₃],    trimethyl-2-acetoxyethylammonium bis(trifluoromethylsulfonyl)imide:-   [(CH₃)₃N⁺CH₂CH₂OC(O)CH3 ⁻N(SO₂CF₃)₂],    trimethyl-2-hydroxyethylammonium bis(perfluorobutanesulfonyl)imide:-   [(CH₃)₃N⁺CH₂CH₂OH ⁻N(SO₂C₄F₉)₂], triethylammonium    bis(perfluoroethanesulfonyl)imide: [Et₃N⁺H ⁻N(SO₂C₂F₅)₂],    tetraethylammonium trifluoromethanesulfonate:-   [CF₃SO₃ ⁻ ⁺NEt₄], tetraethylammonium    bis(trifluoromethanesulfonyl)imide: [(CF₃SO₂)₂N⁻ ⁺NEt₄],    tetramethylammonium tris(trifluoromethanesulfonyl)methide:-   [(CH₃)₄N⁺ ⁻C(SO₂CF₃)₃], tetrabutylammonium    bis(trifluoromethanesulfonyl)imide:-   [(C₄H₉)₄N⁺ ⁻N(SO₂CF₃)₂],    trimethyl-3-perfluorooctylsulfonamidopropylammonium    bis(trifluoromethanesulfonyl)imide:-   [C₈F₁₇SO₂NH(CH₂)₃N⁺(CH₃)₃ ⁻N(SO₂CF₃)₂], 1-hexadecylpyridinium    bis(perfluoroethanesulfonyl)imide:-   [n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻N(SO₂C₂F₅)₂], 1-hexadecylpyridinium    perfluorobutanesulfonate:-   [n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻OSO₂C₄F₉], 1-hexadecylpyridinium    perfluorooctanesulfonate:-   [n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻OSO₂C₈F₁₇], n-butylpyridinium    bis(trifluoromethanesulfonyl)imide:-   [n-C₄H₉-cyc-N⁺C₅H₅ ⁻N(SO₂CF₃)₂], n-butylpyridinium    perfluorobutanesulfonate:-   [n-C₄H₉-cyc-N⁺C₅H₅ ⁻OSO₂C₄F₉], 1,3-ethylmethylimidazolium    bis(trifluoromethanesulfonyl)imide:-   [CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻N(SO₂CF₃)₂], 1,3-ethylmethylimidazolium    nonafluorobutanesulfonate:-   [CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻OSO₂C₄F₉], 1,3-ethylmethylimidazolium    trifluoromethanesulfonate: [CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻OSO₂CF₃],    1,3-ethylmethylimidazolium hexafluorophosphate:-   [CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ PF₆ ⁻], 1,3-ethylmethylimidazolium    tetrafluoroborate:-   [CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ BF₄ ⁻], lithium perfluorobutanesulfonate:    [Li⁺ ⁻OSO₂C₄F₉], lithium trifluoromethanesulfonate: [Li⁺ ⁻OSO₂CF₃],    lithium bis(trifluoromethanesulfonyl)imide: [Li⁺ ⁻N(SO₂CF₃)₂],    lithium tris(trifluoromethanesulfonyl)methide: [Li⁺ ⁻C(SO₂CF₃)₃],    sodium phenylbis(trifluoromethanesulfonyl)methide: [Na⁺    ⁻C(C₆H₅)(SO₂CF₃)₂], octyldimethyl-2-hydroxyethylammonium teflate:    [C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OTeF₅], lithium    permethylmonocarba-closo-dodecaborate: [Li⁺ ⁻CB₁₁(CH₃)₁₂], sodium    monocarba-closo-dodecaborate: [Na⁺ ⁻CB₁₁H₁₂], sodium    tetrakis-(pentafluorophenyl)borate:-   [Na⁺ ⁻B(C₆F₅)₄], octyldimethyl-2-hydroxyethylammonium    methanesulfonate:-   [C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CH₃], tetrabutylphosphonium    perfluorobutanesulfonate: [(C₄H₉)₄P⁺ ⁻OSO₂C₄F₉],    tetraphenylphosphonium bis(trifluoromethanesulfonyl)imide:    [(C₆H₅)₄P⁺ ⁻N(SO₂CF₃)₂], trioctylmethylammonium chloride:    [(C₈H₁₇)₃(CH₃)N⁺Cl⁻], trioctylmethylammonium    trifluoromethanesulfonate: [(C₈H₁₇)₃(CH₃)N⁺ ⁻OSO₂CF₃],    trioctylmethylammonium perfluorobutanesulfonate: [(C₈H₁₇)₃(CH₃)N⁺    ⁻OSO₂C₄F₉], 3-(2-hydroxyethyl)-1-methyl-2-undecylimidazolinium    p-toluenesulfonate:-   [CH₃-cyc-(N⁺C₂H₄N(CH₂CH₂OH)C)C₁₁H₂₃ ⁻OSO₂C₆H₄CH₃],    1-dodecyl-2-ethyl-3-(2-hydroxyethyl)imidazolinium    p-toluenesulfonate:-   [C₁₂H₂₅-cyc-(N⁺C₂H₄N(CH₂CH₂OH)C)C₂H₅ ⁻OSO₂C₆H₄CH₃],    1,2-dimethyl-3-propylimidazolium bis(trifluoromethanesulfonyl)imide,    1,2-dimethyl-3-propylimidazolium    tris(trifluoromethanesulfonyl)methide,    1,2-dimethyl-3-propylimidazolium trifluoromethanesulfonyl    perfluorobutanesulfonylimide, 1-ethyl-3-methylimidazolium    cyanotrifluoromethanesulfonylamide, 1-ethyl-3-methylimidazolium    bis(cyano)trifluoromethanesulfonylmethide,    1-ethyl-3-methylimidazolium    trifluoromethanesulfonylperfluorobutanesulfonylimide,    octyldimethyl-2-hydroxyethylammonium    trifluoromethylsulfonylperfluorobutanesulfonylimide,    2-hydroxyethyltrimethylammonium    trifluoromethylsulfonylperfluorobutanesulfonylimide,    2-methoxyethyltrimethylammonium bis(trifluoromethanesulfonyl)imide    octyldimethyl-2-hydroxyethylammonium    bis(cyano)trifluoromethanesulfonylmethide,    trimethyl-2-acetoxyethylammonium    trifluoromethylsulfonylperfluorobutanesulfonylimide,    1-butylpyridinium    trifluoromethylsulfonylperfluorobutanesulfonylimide,    2-ethoxyethyltrimethylammonium trifluoromethanesulfonate,    1-butyl-3-methylimidazolium perfluorobutanesulfonate,    perfluoro-1-ethyl-3-methylimidazolium    bis(trifluoromethanesulfonyl)imide, 1-ethyl-2-methylpyrazolium    perfluorobutanesulfonate, 1-butyl-2-ethylpyrazolium    trifluoromethanesulfonate, N-ethylthiazolium    bis(trifluoromethanesulfonyl)imide, N-ethyloxazolium    bis(trifluoromethanesulfonyl)imide, and 1-butylpyrimidinium    perfluorobutanesulfonylbis(trifluoromethanesulfonyl)-methide,    1,3-ethylmethylimidazolium hexafluorophosphate,    1,3-ethylmethylimidazolium tetrafluoroborate, and mixtures thereof.

Preferred ionic salt antistats includeoctyldimethyl-2-hydroxyethylammonium bis(trifluoromethylsulfonyl)imide:

-   [C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻N(SO₂CF₃)₂],    octyldimethyl-2-hydroxyethylammonium perfluorobutanesulfonate:-   [C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂C₄F₉],    octyldimethyl-2-hydroxyethylammonium trifluoromethanesulfonate:-   [C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CF₃],    octyldimethyl-2-hydroxyethylammonium    tris(trifluoromethanesulfonyl)methide:-   [C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻C(SO₂CF₃)₃],    trimethyl-2-acetoxyethylammonium bis(trifluoromethylsulfonyl)imide:-   [(CH₃)₃N⁺CH₂CH₂OC(O)CH3 ⁻N(SO₂CF₃)₂],    trimethyl-2-hydroxyethylammonium bis(perfluorobutanesulfonyl)imide:-   [(CH₃)₃N⁺CH₂CH₂OH ⁻N(SO₂C₄F₉)₂], triethylammonium    bis(perfluoroethanesulfonyl)imide: [Et₃N⁺H ⁻N(SO₂C₂F₅)₂],    tetraethylammonium trifluoromethanesulfonate:-   [CF₃SO₃ ⁻ ⁺NEt₄], tetraethylammonium    bis(trifluoromethanesulfonyl)imide: [(CF₃SO₂)₂N⁻ ⁺NEt₄],    tetramethylammonium tris(trifluoromethanesulfonyl)methide:-   [(CH₃)₄N⁺ ⁻C(SO₂CF₃)₃], tetrabutylammonium    bis(trifluoromethanesulfonyl)imide:-   [(C₄H₉)₄N⁺ ⁻N(SO₂CF₃)₂],    trimethyl-3-perfluorooctylsulfonamidopropylammonium    bis(trifluoromethanesulfonyl)imide:-   [C₈F₁₇SO₂NH(CH₂)₃N⁺(CH₃)₃ ⁻N(SO₂CF₃)₂], 1-hexadecylpyridinium    bis(perfluoroethanesulfonyl)imide:-   [n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻N(SO₂C₂F₅)₂], 1-hexadecylpyridinium    perfluorobutanesulfonate:-   [n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻OSO₂C₄F₉], 1-hexadecylpyridinium    perfluorooctanesulfonate:-   [n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻OSO₂C₈F₁₇], n-butylpyridinium    bis(trifluoromethanesulfonyl)imide:-   [n-C₄H₉-cyc-N⁺C₅H₅ ⁻N(SO₂CF₃)₂], n-butylpyridinium    perfluorobutanesulfonate:-   [n-C₄H₉-cyc-N⁺C₅H₅ ⁻OSO₂C₄F₉], 1,3-ethylmethylimidazolium    bis(trifluoromethanesulfonyl)imide:-   [CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻N(SO₂CF3)₂], 1,3-ethylmethylimidazolium    nonafluorobutanesulfonate:-   [CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻OSO₂C₄F₉], 1,3-ethylmethylimidazolium    trifluoromethanesulfonate: [CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻OSO₂CF₃],    lithium perfluorobutanesulfonate: [Li⁺ ⁻OSO₂C₄F₉], lithium    trifluoromethanesulfonate: [Li⁺ ⁻OSO₂CF₃], lithium    bis(trifluoromethanesulfonyl)imide: [Li⁺N(SO₂CF₃)₂],    tetrabutylphosphonium perfluorobutanesulfonate: [(C₄H₉)₄P⁺    ⁻OSO₂C₄F₉], octyldimethyl-2-hydroxyethylammonium methanesulfonate:-   [C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CH₃],    1-dodecyl-2-ethyl-3-(2-hydroxyethyl)imidazolinium    p-toluenesulfonate:-   [C₁₂H₂₅-cyc-(N⁺C₂H₄N(CH₂CH₂OH)C)C₂H₅ ⁻OSO₂C₆H₄CH₃],    1,3-ethylmethylimidazolium tetrafluoroborate, and mixtures thereof.

More preferred ionic salt antistats includeoctyldimethyl-2-hydroxyethylammonium bis(trifluoromethylsulfonyl)imide,octyldimethyl-2-hydroxyethylammonium perfluorobutanesulfonate,octyldimethyl-2-hydroxyethylammonium trifluoromethanesulfonate,triethylammonium bis(perfluoroethanesulfonyl)imide, tetraethylammoniumtrifluoromethanesulfonate,trimethyl-3-perfluorooctylsulfonamidopropylammoniumbis(trifluoromethanesulfonyl)imide, 1,3-ethylmethylimidazoliumnonafluorobutanesulfonate, 1,3-ethylmethylimidazoliumbis(trifluoromethanesulfonyl)imide, 1,3-ethylmethylimidazoliumtrifluoromethanesulfonate, tetrabutylphosphoniumperfluorobutanesulfonate, and mixtures thereof.

Most preferred ionic salt antistats includeoctyldimethyl-2-hydroxyethylammonium bis(trifluoromethylsulfonyl)imide,octyldimethyl-2-hydroxyethylammonium trifluoromethanesulfonate,octyldimethyl-2-hydroxyethylammonium nonafluorobutanesulfonate,triethylammonium bis(perfluoroethanesulfonyl)imide,1,3-ethylmethylimidazolium nonafluorobutanesulfonate,1,3-ethylmethylimidazolium bis(trifluoromethanesulfonyl)imide,1,3-ethylmethylimidazolium trifluoromethanesulfonate,tetrabutylphosphonium perfluorobutanesulfonate, and mixtures thereof,with further preferences being in accordance with the general cation andanion preferences set forth above.

Fluorochemical Repellents

Suitable fluorochemical repellency-imparting additives or repellents foruse in the composition of the invention are those that comprise at leastone fluorochemical group, preferably, at least one fluoroaliphatic orfluoroalicyclic group. Such fluorochemicals include any of thefluorochemical group-containing polymeric and oligomeric compounds knownin the art to impart water and oil repellency to substrates. Thesepolymeric and oligomeric fluorochemicals typically comprise one or morefluorochemical groups that contain a perfluorinated carbon chain havingfrom 3 to about 20 carbon atoms, more preferably from about 4 to about12 carbon atoms. These fluorochemical groups can contain straight chain,branched chain, or cyclic fluorinated alkylene groups or any combinationthereof. The fluorochemical groups can optionally contain catenary(i.e., in-chain) heteroatoms such as oxygen, divalent or hexavalentsulfur, or nitrogen. Fully-fluorinated groups are preferred, buthydrogen or chlorine atoms can also be present as substituents, providedthat no more than one atom of either is present for every two carbonatoms. It is additionally preferred that any fluorochemical groupcontain at least about 40% fluorine by weight, more preferably at leastabout 50% fluorine by weight. The terminal portion of the group isgenerally fully-fluorinated, preferably containing at least 7 fluorineatoms, e.g., CF₃CF₂CF₂—, (CF₃)₂CF—, SF₅CF₂—. Perfluorinated aliphaticgroups (i.e., those of the formula C_(n)F_(2n+1)—) are the mostpreferred fluorochemical groups.

Representative examples of suitable fluorochemicals includefluorochemical urethanes, ureas and substituted ureas, esters, ethers,alcohols, epoxides, allophanates, amides, amines (and salts thereof),acids (and salts thereof), carbodiimides, guanidines, oxazolidinones,isocyanurates, piperazines, aminoalcohols, sulfones, imides, biurets,acrylate and methacrylate homopolymers and copolymers, siloxanes,alkoxysilanes, chlorosilanes, and mixtures thereof.

Representative fluorochemical group-containing polymers useful in thepresent invention include fluorochemical acrylate and methacrylatehomopolymers or copolymers containing fluorochemical acrylate monomersinterpolymerized with monomers such as methyl methacrylate, butylacrylate, octadecylmethacrylate, acrylate and methacrylate esters ofoxyalkylene and polyoxyalkylene polyol oligomers (e.g., oxyethyleneglycol dimethacrylate, polyoxyethylene glycol dimethacrylate, methoxyacrylate, and polyoxyethylene acrylate), glycidyl methacrylate,ethylene, butadiene, styrene, isoprene, chloroprene, vinyl acetate,vinyl chloride, vinylidene chloride, vinylidene fluoride, acrylonitrile,vinyl chloroacetate, vinylpyridine, vinyl alkyl ethers, vinyl alkylketones, acrylic acid, methacrylic acid, 2-hydroxyethylacrylate,N-methylolacrylamide, 2-(N,N,N-trimethylammonium)ethyl methacrylate, and2-acrylamido-2-methylpropanesulfonic acid (AMPS). The relative amountsof various comonomers used can generally be selected empirically,depending on the substrate to be treated, the properties desired, andthe mode of application to the substrate. Useful fluorochemicals alsoinclude blends of the various fluorochemicals described above.

Also useful in the present invention are blends of fluorochemicals withfluorine-free extender compounds, such as siloxanes, (meth)acrylate andsubstituted acrylate polymers and copolymers,N-methylolacrylamide-containing acrylate polymers, urethanes, blockedisocyanate-containing polymers and oligomers, condensates orprecondensates of urea or melamine with formaldehyde, glyoxal resins,condensates of fatty acids with melamine or urea derivatives,condensates of fatty acids with polyamides and their epichlorohydrinadducts, waxes, polyethylene, chlorinated polyethylene, alkyl ketenedimers, esters, and amides. Blends of these fluorine-free extendercompounds can also be used. The relative amount of extender compound tofluorochemical is not critical. However, the overall composition of thefluorochemical treatment generally contains, relative to the amount ofsolids present in the system, at least about 3 weight percent,preferably at least about 5 weight percent, carbon-bound fluorine in theform of said fluorochemical groups.

Many fluorochemicals, including blends that include fluorine-freeextender molecules such as those described above, are commerciallyavailable as ready-made formulations. Such products are sold, forexample, as Scotchgard™ brand Carpet Protector (manufactured by 3M Co.,Saint Paul, Minn.) and as Zonyl™ brand Carpet Treatment (manufactured byE.I. du Pont de Nemours and Company, Wilmington, Del.).

Useful fluorochemicals are described in European Pat. No. 0 613 462(Minnesota Mining and Manufacturing Company) and in U.S. Pat. No.3,728,151 (Sherman et al.), U.S. Pat. No. 3,816,229 (Bierbrauer), U.S.Pat. No. 3,896,035 (Schultz et al.), U.S. Pat. No. 3,901,727 (Loudas),U.S. Pat. No. 3,916,053 (Sherman et al.), U.S. Pat. No. 4,043,923(Loudas), U.S. Pat. No. 4,043,964 (Sherman et al.), U.S. Pat. No.4,264,484 (Patel), U.S. Pat. No. 4,624,889 (Bries), U.S. Pat. No.5,274,159 (Pellerite et al.), U.S. Pat. No. 5,380,778 (Buckanin), andU.S. Pat. No. 5,451,622 (Boardman et al.), the descriptions of which areincorporated herein by reference.

Fluorochemical repellents suitable for use as polymer melt additives arepreferably stable at temperatures of 250° C. and above (more preferably,300° C. and above), are preferably miscible with the insulating materialat the melt processing temperature, and are preferably capable ofmigration to the surface of the insulating material. Thus, a preferredclass of fluorochemical repellents, useful both in topical treatmentsand as polymer melt (or other bulk polymer) additives, includesfluorochemical oxazolidinone compositions or fluorochemicaloxazolidinones comprising normally solid, water-insoluble,fluoroaliphatic radical-containing 2-oxazolidinone compounds, thecompounds comprising one or more 2-oxazolidinone moieties,

at least one of which has a monovalent fluoroaliphatic radical, R_(f),bonded to the 5-position carbon atom thereof by an organic linkinggroup.

A preferred subclass of such fluoroaliphatic radical-containingoxazolidinone compounds is that represented by Formula II below:

where each R¹ is independently hydrogen or an organic radical, whichorganic radical can contain -Q-R_(f) where Q is a linking group andR_(f) is a fluoroaliphatic radical that can optionally contain one ormore catenary (in-chain) heteroatoms such as oxygen; each R² isindependently an organic radical, which organic radical can contain-Q-R_(f) where Q and R_(f) are as defined above; with the proviso thatthere is at least one R_(f) radical in one of R¹ and R²; each A isindependently an organic radical; a is zero or 1; b is a number from 0to about 6; c is 0, 1, or 2; and the sum of a+b+c is at least 1.Preferably, R₁ is an organic radical that contains -QR_(f), where R_(f)is a perfluoroalkyl group having from about 3 to about 20 carbon atoms(preferably, from about 4 to about 12 carbon atoms), and Q comprises aheteroatom-containing group, an organic group, or a combination thereof(preferably, Q is —SO₂N(R′)(CH₂)_(k)—, —(CH₂)_(k)—, —CON(R′)(CH₂)_(k)—,or —(CH₂)_(k)SO₂N(R′)(CH₂)_(k)—, where R′ is hydrogen, phenyl, or ashort chain (up to about 6 carbon atoms) alkyl group (preferably, methylor ethyl), and each k is independently an integer from 1 to about 20); ais 1; b is 0; c is 0; and A is an alkyl group having from about 12 toabout 22 carbon atoms. Formula II represents individual compounds ormixtures of compounds, for example, as they are obtained as productsfrom reactions used in their preparation.

Such fluorochemical oxazolidinone compositions can be prepared usingknown organic reactions, for example, by the reaction of epoxides orhalohydrins (for example, chlorohydrins or bromohydrins) with organicisocyanates in each which reaction at least one of the reactantscontains an R_(f) radical. The reactions can be carried out stepwise byreacting the halohydrin with the isocyanate under urethane bond-formingconditions, for example, 20° C. to 100° C. for about 1 to 24 hours, toform a urethane intermediate, followed by addition of a base andreaction at about 20° C. to 100° C. for about 1 to 24 hours to form theoxazolidinone composition. Alternatively, an epoxide can be reacted withan isocyanate in the presence of a catalyst, such as diethyl zinc, toform the oxazolidinone directly.

Suitable fluorochemical oxazolidinones and methods for their preparationare further described in U.S. Pat. Nos. 5,025,052 and 5,099,026 (Crateret al.), the descriptions of which are incorporated herein by reference.

Other preferred fluorochemical repellents, useful both in topicaltreatments and as polymer melt (or other bulk polymer) additives,include those described in U.S. Pat. No. 3,899,563 (Oxenrider et al.),U.S. Pat. No. 4,219,625 (Mares et al.), U.S. Pat. No. 5,560,992 (Sargentet al.), and U.S. Pat. No. 5,681,963 (Liss); International PatentPublication Nos. WO 97/22576, WO 97/22659, and WO 97/22660 (E. I. duPont de Nemours and Company); Japanese Patent Publication Nos. 3-041160(Kao Corporation) and 9-323956 (Wako Junyaku Kogyo Co.); andInternational Patent Publication No. WO 99/05345 (Minnesota Mining andManufacturing Company), the descriptions of which are incorporatedherein by reference.

Of these, particularly preferred are the fluorochemical group-containingderivatives of long-chain (preferably, having at least about 30 carbonatoms; more preferably, dimer and trimer, as defined below) acids,alcohols, and amines. A preferred class of such derivatives includes thecompounds or mixtures of compounds represented by the formulas:{(R_(f))_(n)-Q-O—C(O)}_(p)-A{(R_(f))_(n)-Q-C(O)—O}_(p)-A′{(R_(f))_(n)-Q-N(R)—C(O)}_(p)-A{(R_(f))_(n)-Q-C(O)—N(R)}_(p)-A′wherein R_(f) is a fluorinated alkyl group (which can optionally containone or more catenary (in-chain) heteroatoms such as oxygen) bondedthrough carbon; n is 1 or 2; Q is a divalent or trivalent linking groupor a covalent bond; p is 2 or more, up to the valency of A or A′; R is ahydrogen atom or is a substituted or unsubstituted alkyl group; A is theresidue of a dimer or trimer acid; and A′ is the residue of a dimerdiol, a dimer diamine, a trimer triol, or a trimer triamine. Preferably,R_(f) is a perfluoroalkyl group having from about 3 to about 20 carbonatoms (preferably, from about 4 to about 12 carbon atoms); R is an alkylgroup having from 1 to 6 carbon atoms; Q is —SO₂N(R′)(CH₂)_(k)—,—(CH₂)_(k)—, —CON(R′)(CH₂)_(k)—, or —(CH₂)_(k)SO₂N(R′)(CH₂)_(k)—, whereR′ is hydrogen, phenyl, or a short chain (up to about 6 carbon atoms)alkyl group (preferably, methyl or ethyl), and each k is independentlyan integer from 1 to about 20; A is the residue of a dimer acid; and A′is the residue of a dimer diol or dimer diamine. The esters and“reverse” esters are preferred over the amides and “reverse” amides.

Such fluorochemical group-containing dimer and trimer acid esters can beprepared by heating a fluorochemical alcohol with either a dimer acid ora trimer acid in the presence of a standard acid catalyst, or by firstmaking an acid chloride of the dimer/trimer acid and then reacting theacid chloride with a fluorochemical alcohol at a slightly elevatedtemperature (for example, 50-60° C.) in the presence of an acidscavenger. Fluorochemical group-containing “reverse” esters can beprepared by reacting a fluorochemical carboxylic acid with a dimer diol,using the same synthetic procedure as described for preparing esters.Fluorochemical group-containing amides can be prepared by reacting afluorochemical amine with a dimer or trimer acid by heating thecomponents together neat at an elevated temperature (at least about 220°C.), or by first making an acid chloride of the dimer/trimer acid andthen reacting the acid chloride with a fluorochemical amine at aslightly elevated temperature. Fluorochemical group-containing “reverse”amides can be prepared by reacting a fluorochemical carboxylic acid witha dimer amine, using the same synthetic procedure as described forpreparing esters.

The terms “dimer acid” and “trimer acid” refer to oligomerizedunsaturated fatty acid products of relatively high molecular weight. Theproducts are mixtures comprising various ratios of a variety of large orrelatively high molecular weight substituted cyclohexenecarboxylicacids, predominately 36-carbon dibasic acids (dimer acid) and 54-carbontribasic acids (trimer acid), with no single structure sufficient tocharacterize each. Component structures can be acyclic, cyclic(monocyclic or bicyclic), or aromatic.

Dimer and trimer acids (for use in preparing the above-describedfluorochemical repellents) can be prepared by condensing unsaturatedmonofunctional carboxylic acids such as oleic, linoleic, soya, or talloil acid through their olefinically unsaturated groups, in the presenceof catalysts such as acidic clays. Dimer/trimer acids are commerciallyavailable from a variety of vendors, including Henkel Corporation/EmeryGroup (as EMPol™ 1008, 1061, 1040 and 1043) and Unichema North America(as Pripol™ 1004 and 1009). Dimer diols and diamines can be made fromthe corresponding dimer acid by methods well known in the art. Dimerdiols are commercially available from Henkel Corp./Emery Group as Empol™1070 and 1075 diols. Dimer amines are commercially available from WitcoCorp., for example, as Kemamine™ DP-3695 amine.

Insulating Materials

Insulating materials that are suitable for topical treatment includematerials that have relatively low surface and bulk conductivity andthat are prone to static charge buildup. Such materials include bothsynthetic and naturally-occurring polymers (or the reactive precursorsthereof, for example, mono- or multifunctional monomers or oligomers)that can be either organic or inorganic in nature, as well as ceramics,glasses, and ceramic/polymer composites or ceramers (or the reactiveprecursors thereof).

Suitable synthetic polymers (which can be either thermoplastic orthermoset) include commodity plastics such as, for example, poly(vinylchloride), polyethylenes (high density, low density, very low density),polypropylene, and polystyrene; engineering plastics such as, forexample, polyesters (including, for example, poly(ethyleneterephthalate) and poly(butylene terephthalate)), polyamides (aliphatic,amorphous, aromatic), polycarbonates (for example, aromaticpolycarbonates such as those derived from bisphenol A),polyoxymethylenes, polyacrylates and polymethacrylates (for example,poly(methyl methacrylate)), some modified polystyrenes (for example,styrene-acrylonitrile (SAN) and acrylonitrile-butadiene-styrene (ABS)copolymers), high-impact polystyrenes (SB), fluoroplastics, and blendssuch as poly(phenylene oxide)-polystyrene and polycarbonate-ABS;high-performance plastics such as, for example, liquid crystallinepolymers (LCPs), polyetherketone (PEEK), polysulfones, polyimides, andpolyetherimides; thermosets such as, for example, alkyd resins, phenolicresins, amino resins (for example, melamine and urea resins), epoxyresins, unsaturated polyesters (including so-called vinyl esters),polyurethanes, allylics (for example, polymers derived fromallyldiglycolcarbonate), fluoroelastomers, and polyacrylates; and thelike and blends thereof. Suitable naturally occurring polymers includeproteinaceous materials such as silk, wool, and leather; and cellulosicmaterials.

Thermoplastic and thermoset polymers, including those described above,are preferred insulating materials, as such polymers can either betopically treated with the antistat/repellent combination or can becombined with it (in bulk) to form a blend. Thermoplastic polymers aremore preferred in view of their melt processability. Preferably, thethermoplastic polymers are melt processable at elevated temperatures,for example, above about 150° C. (more preferably, above about 250° C.;even more preferably, above about 280° C.; most preferably, above about320° C.). Preferred thermoset polymers include polyurethanes, epoxyresins, and unsaturated polyesters. Preferred thermoplastic polymersinclude, for example, polypropylene, polyethylene, copolymers ofethylene and one or more alpha-olefins (for example,poly(ethylene-butene) and poly(ethylene-octene)), polyesters,polyurethanes, polycarbonates, polyetherimides, polyimides,polyetherketones, polysulfones, polystyrenes, ABS copolymers,polyamides, fluoroelastomers, and blends thereof. More preferred arepolypropylene, polyethylene, polyesters, poly(ethylene-octene),polyurethanes, polycarbonates, and blends thereof, with polypropylene,polyethylene, poly(ethylene-octene), polyurethanes, and blends thereofbeing most preferred.

Preparation and Use of Composition

Preferably, the composition of the invention can be prepared by (a)combining at least one ionic salt antistat, at least one fluorochemicalrepellent, and at least one thermoplastic polymer (optionally, alongwith other additives) and then melt processing the resultingcombination; or (b) combining at least one ionic salt antistat, at leastone fluorochemical repellent, and at least one thermosetting polymer orceramer or the reactive precursors thereof (optionally, along with otheradditives) and then allowing the resulting combination to cure,optionally with the application of heat or actinic radiation.Alternative processes for preparing the composition include, forexample, (c) applying a treatment composition comprising at least oneionic salt antistat and at least one fluorochemical repellent to atleast a portion of at least one surface of at least one insulatingmaterial; (d) dissolving at least one ionic salt antistat, at least onefluorochemical repellent, and at least one insulating material in atleast one solvent and then casting or coating the resulting solution andallowing evaporation of the solvent, optionally with the application ofheat; and (e) combining at least one ionic salt antistat, at least onefluorochemical repellent, and at least one monomer (optionally, alongwith other additives) and then allowing polymerization of the monomer tooccur, optionally in the presence of at least one solvent and optionallywith the application of heat or actinic radiation. If desired, theantistat and repellent can be utilized separately, for example, one canbe added prior to melt processing, and the other can then be topicallyapplied to the resulting melt-processed combination. Separate topicaltreatments, etc., are also possible.

To form a melt blend by melt processing, the ionic salt antistat(s) andfluorochemical repellent(s) can be, for example, intimately mixed withpelletized or powdered polymer and then melt processed by known methodssuch as, for example, molding, melt blowing, melt spinning, or meltextrusion. The antistat and repellent additives can be mixed directlywith the polymer or they can be mixed with the polymer in the form of a“master batch” (concentrate) of the additives in the polymer. Ifdesired, an organic solution of the additives can be mixed with powderedor pelletized polymer, followed by drying (to remove solvent) and thenby melt processing. Alternatively, the additives can be injected into amolten polymer stream to form a blend immediately prior to, for example,extrusion into fibers or films or molding into articles.

After melt processing, an annealing step can be carried out to enhancethe development of antistatic and repellent characteristics. In additionto, or in lieu of, such an annealing step, the melt processedcombination (for example, in the form of a film or a fiber) can also beembossed between two heated rolls, one or both of which can bepatterned. An annealing step typically is conducted below the melttemperature of the polymer (for example, in the case of polyamide, atabout 150-220° C. for a period of about 30 seconds to about 5 minutes).In some cases, the presence of moisture can improve the effectiveness ofthe ionic salt antistat(s), although the presence of moisture is notnecessary in order for antistatic characteristics to be obtained.

The ionic salt antistat(s) and fluorochemical repellent(s) can be addedto thermoplastic or thermosetting polymer (or, alternatively, to otherinsulating material) in amounts sufficient to achieve the desiredantistatic and repellency properties for a particular application. Theamounts can be determined empirically and can be adjusted as necessaryor desired to achieve the antistatic and repellency properties withoutcompromising the properties of the polymer (or other insulatingmaterial). Generally, the ionic salt antistat(s) and the fluorochemicalrepellent(s) can each be added in amounts ranging from about 0.1 toabout 10 percent by weight (preferably, from about 0.5 to about 2percent; more preferably, from about 0.75 to about 1.5 percent) based onthe weight of polymer (or other insulating material).

In topical treatment of an insulating material, the combination of ionicsalt antistat(s) and fluorochemical repellent(s) can be employed aloneor in the form of aqueous suspensions, emulsions, or solutions, or asorganic solvent (or organic solvent/water) solutions, suspensions, oremulsions. Useful organic solvents include chlorinated hydrocarbons,alcohols (for example, isopropyl alcohol), esters, ketones (for example,methyl isobutyl ketone), and mixtures thereof. Generally, the solventsolutions can contain from about 0.1 to about 50 percent, or even up toabout 90 percent, by weight non-volatile solids (based on the totalweight of the components). Aqueous suspensions, emulsions, or solutionsare generally preferred and generally can contain a non-volatile solidscontent of about 0.1 to about 50 percent, preferably, about 1 to about10 percent, by weight (based on the total weight of the components).Alternatively, however, topical treatment can be carried out by applying(to at least a portion of at least one surface of at least oneinsulating material) a topical treatment composition that comprises atleast one ionic salt antistat that is liquid at the use or treatmenttemperature. Such a topical treatment process can involve the use of theneat liquid ionic salt antistat, without added solvent, and is thuspreferred from an environmental perspective over the use of organicsolvent solutions of the antistat/repellent combination.

The topical treatment compositions comprising the antistat/repellentcombination can be applied to an insulating material by standard methodssuch as, for example, spraying, padding, dipping, roll coating,brushing, or exhaustion (optionally followed by the drying of thetreated material to remove any remaining water or solvent). The materialcan be in the form of molded or blown articles, sheets, fibers (as suchor in aggregated form, for example, yarn, toe, web, or roving, or in theform of fabricated textiles such as carpets), woven and nonwovenfabrics, films, etc. If desired, the antistat/repellent combination canbe co-applied with conventional fiber treating agents, for example, spinfinishes or fiber lubricants.

The topical treatment compositions can be applied in an amountsufficient to achieve the desired antistatic and repellency propertiesfor a particular application. This amount can be determined empiricallyand can be adjusted as necessary or desired to achieve the antistaticand repellency properties without compromising the properties of theinsulating material.

Any of a wide variety of constructions can be made from the compositionof the invention, and such constructions will find utility in anyapplication where some level of antistatic and repellencycharacteristics is required. For example, the composition of theinvention can be used to prepare films and molded or blown articles, aswell as fibers (for example, melt-blown or melt-spun fibers, includingmicrofibers) that can be used to make woven and nonwoven fabrics. Suchfilms, molded or blown articles, fibers, and fabrics exhibit antistaticand water and oil repellency (and soil resistance) characteristics undera variety of environmental conditions and can be used in a variety ofapplications.

For example, molded articles comprising the composition of the inventioncan be prepared by standard methods (for example, by high temperatureinjection molding) and are particularly useful as, for example, headlampcovers for automobiles, lenses (including eyeglass lenses), casings orcircuit boards for electronic devices (for example, computers), screensfor display devices, windows (for example, aircraft windows), and thelike. Films comprising the composition of the invention can be made byany of the film making methods commonly employed in the art. Such filmscan be nonporous or porous (the latter including films that aremechanically perforated), with the presence and degree of porosity beingselected according to the desired performance characteristics. The filmscan be used as, for example, photographic films, transparency films foruse with overhead projectors, tape backings, substrates for coating, andthe like.

Fibers comprising the composition of the invention can be used to makewoven or nonwoven fabrics that can be used, for example, in makingmedical fabrics, medical and industrial apparel, fabrics for use inmaking clothing, home furnishings such as rugs or carpets, and filtermedia such as chemical process filters or respirators. Nonwoven webs orfabrics can be prepared by processes used in the manufacture of eithermelt-blown or spunbonded webs. For example, a process similar to thatdescribed by Wente in “Superfine Thermoplastic Fibers,” Indus. Eng'gChem. 48, 1342 (1956) or by Wente et al. in “Manufacture of SuperfineOrganic Fibers,” Naval Research Laboratories Report No. 4364 (1954) canbe used. Multi-layer constructions made from nonwoven fabrics enjoy wideindustrial and commercial utility, for example, as medical fabrics. Themakeup of the constituent layers of such multi-layer constructions canbe varied according to the desired end-use characteristics, and theconstructions can comprise two or more layers of melt-blown andspunbonded webs in many useful combinations such as those described inU.S. Pat. No. 5,145,727 (Potts et al.) and U.S. Pat. No. 5,149,576(Potts et al.), the descriptions of which are incorporated herein byreference. In multi-layer constructions, the ionic salt antistat(s) andfluorochemical repellent(s) can be used in combination in one or morelayers, or each can be independently segregated in one or more layers.For example, in a spunbonded/melt-blown/spunbonded (“SMS”) three-layerconstruction, the ionic salt antistat(s) can be used in one or bothspunbonded layers, and the fluorochemical repellent(s) can be used inthe melt-blown layer, to impart both antistatic and repellencycharacteristics to the overall construction.

The ionic salt antistat(s) and fluorochemical repellent(s) used in thecomposition of the invention can also find utility as additives tocoatings (for example, polymer or ceramer coatings). Such coatings canbe antistatic, water- and oil-repellent, and scratch-resistant (as wellas soil-resistant) and can be used in the photographic industry or asprotective coatings for optical or magnetic recording media.

If desired, the composition of the invention can further contain one ormore conventional additives commonly used in the art, for example, dyes,pigments, antioxidants, ultraviolet stabilizers, flame retardants,surfactants, plasticizers, tackifiers, fillers, and mixtures thereof. Inparticular, performance enhancers (for example, polymers such aspolybutylene) can be utilized to improve the antistatic and/orrepellency characteristics in, for example, melt additive polyolefinapplications.

Objects and advantages of this invention are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this invention. In the examples,where weight percent or parts by weight are indicated, these are basedon the weight of the entire composition unless indicated otherwise.

EXAMPLES

Glossary

Antistats

HTS 905 and 905A—Larostat™ HTS 905 or 905A (anhydrous),C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CH₃, available from BASF, Gurnee, Ill.

HTS-904—3-(2-hydroxyethyl)-1-methyl-2-undecylimidazoliniump-toluenesulfonate, available from BASF, Gurnee, Ill.

Lithium perfluorobutanesulfonate—available from 3M, St. Paul, Minn.

Anstex™ SA-300—an antistatic melt additive agent, octadecanoic acid2-[(2-hydroxyethyl)octadecylamino]ethyl ester, available from TOHOchemical Industry Co., Japan.

Aluminum Stearate—available from All Chemie Ltd., Mt. Pleasant, S.C.

Lithium Stearate—available from ACROS Organics USA, Pittsburg, Pa.

Glycerol Monostearate—available from Sigma-Aldrich, Milwaukee, Wis.

Aliquat™ 336—Methyltrioctylammonium chloride, available fromSigma-Aldrich, Milwaukee, Wis., or from Henkel Corp., Ambler, Pa.

Starting Materials for Antistats

HQ-115—LiN(SO₂CF₃)₂ available from 3M, St. Paul, Minn.

PBSF—Perfluorobutanesulfonyl fluoride, available from Sigma-Aldrich,Milwaukee, Wis.

Lithium triflate—Lithium trifluoromethanesulfonate, available fromSigma-Aldrich, Milwaukee, Wis.

FC-24—Trifluoromethanesulfonic acid, available from 3M, St. Paul, Minn.

FC-754—Trimethyl-3-perfluorooctylsulfonamidopropylammonium chloride,available from 3M, St. Paul, Minn.

FC-94—Lithium perfluorooctanesulfonate, available from 3M, St. Paul,Minn.

Cetylpyridinium chloride monohydrate—1-Hexadecylpyridinium chloride,available from Research Organics, Cleveland, Ohio.

1,3-Ethylmethylimidazolium chloride—Available from Sigma-Aldrich,Milwaukee, Wis.

Silver triflate—Silver trifluoromethanesulfonate, available fromSigma-Aldrich, Milwaukee, Wis.

AgBF₄—Silver tetrafluoroborate, available from Sigma-Aldrich, Milwaukee,Wis.

NH₄PF₆—Ammonium hexafluorophosphate, available from Sigma-Aldrich,Milwaukee, Wis.

Acetylcholine chloride—CH₃CO₂CH₂CH₂N(CH₃)₃Cl, available from ResearchOrganics, Cleveland, Ohio.

Choline chloride—HOCH₂CH₂N(CH₃)₃Cl, available from Sigma-Aldrich,Milwaukee, Wis.

Fluorochemical Repellents

FC-808—A fluorochemical emulsion of a polymeric fluoroaliphatic ester(80 weight percent in water) for fluid repellency, available from 3M,St. Paul, Minn.

Starting Materials for Fluorochemical Repellents

MeFOSE alcohol—C₈F₁₇SO₂N(CH₃)CH₂CH₂OH, having an equivalent weight of540, made in two stages by reacting POSF perfluorooctanesulfonylfluoride with methylamine and ethylenechlorohydrin, using a proceduresimilar to that described in Example 1 of U.S. Pat. No. 2,803,656(Ahlbrecht et al.).

Empol™ 1008 acid—a distilled and hydrogenated dimer acid based on oleicacid, having an acid equivalent weight of 305 as determined bytitration, commercially available from Henkel Corp./Emery Group,Cincinnati, Ohio.

Pripol™ 1048 acid—a hydrogenated distilled dimer/trimer acid based onoleic acid, commercially available from Unichema North America, Chicago,Ill.

Thermoplastic Polymers

PP3505—ESCORENE™ PP3505 polypropylene, having a 400 melt index flowrate, available from Exxon Chemical Co., Baytown, Tex.

Montell H422PP—a granular polypropylene polymer (with peroxide) havingan 850 melt flow index, available from Montell North America,Wilmington, Del.

PB0200—polybutylene, available from Shell Chemical Co., Houston, Tex.

PB8340—copolymer of 1-butene and ethylene, available from Shell ChemicalCo., Houston, Tex.

PE6806—ASPUN™ 6806 polyethylene, having a melt flow index of 105 g/10min (as measured by Test Method ASTM D-1238) and having a peak meltingpoint of 124.8° C., available from Dow Chemical Co., Midland, Mich.

PS440-200—MORTHANE™ PS440-200 urethane, available from Morton ThiokolCorp., Chicago, Ill.

Test Methods

Test Method I—Melting Point Determination

The melting points of salts were determined by differential scanningcalorimetry (DSC) using a 20° C. per minute temperature ramp. The peakmaximum of the melt transition was taken as the melting point (Tm).Where multiple melt transitions were observed, the peak associated withthe largest area melt transition was taken as the melting point.

Test Method II—Onset of Thermal Decomposition Determination

The onset of thermal decomposition of each salt was determined bythermal gravimetric analysis (TGA) under an inert nitrogen atmosphereusing a 10° C. per minute temperature ramp. The value of the onsettemperature was determined by finding the intersection of theextrapolated tangent at the baseline preceding onset and theextrapolated tangent at the inflection point associated with the stepchange in sample weight.

Test Method III—Static Charge Dissipation Test

The static charge dissipation characteristics of nonwoven fabrics,films, and molded sheets were determined with this method. The testmaterials were cut into 9 cm by 12 cm samples and conditioned atrelative humidities (RH) of about 10 percent, 25 percent, and 50 percentfor at least 12 hours. The materials were tested at temperatures thatranged from 22-25° C. The static charge dissipation time was measuredaccording to Federal Test Method Standard 10113, Method 4046,“Antistatic Properties of Materials”, using an ETS Model 406C StaticDecay Test Unit (manufactured by Electro-Tech Systems, Inc., Glenside,Pa.). This apparatus induces an initial static charge (Average InducedElectrostatic Charge) on the surface of the flat test material by usinghigh voltage (5000 volts), and a fieldmeter allows observation of thedecay time of the surface voltage from 5000 volts (or whatever theinduced electrostatic charge was) to 10 percent of the initial inducedcharge. This is the static charge dissipation time. The lower the staticcharge dissipation time, the better the antistatic properties are of thetest material. All reported values of the static charge dissipationtimes in this invention are averages (Average Static Decay Rate) over atleast 3 separate determinations. Values reported as >10, >60, or >100seconds indicate that the material tested has an initial static chargewhich cannot be removed by surface conduction and is not antistatic.When the material tested did not accept a charge of about 3000 volts ormore, it was not considered to have charged sufficiently to beantistatic.

Test Method IV—Surface Resistivity Test

This test was conducted according to the procedure of ASTM StandardD-257, “D.C. Resistance or Conductance of Insulating Materials”. Thesurface resistivity was measured under the conditions of this testmethod using an ETS Model 872 Wide Range Resistance Meter fitted with aModel 803B probe (Electro-Tech Systems, Inc., Glenside, Pa.). Thisapparatus applies an external voltage of 100 volts across two concentricring electrodes contacting the flat test material, and provides surfaceresistivity readings in ohm/square units.

Test Method V—Water Repellency Test

Nonwoven web samples were evaluated for water repellency using 3M WaterRepellency Test V for Floorcoverings (February 1994), available from 3MCompany. In this test, samples are challenged to penetrations by blendsof deionized water and isopropyl alcohol (IPA). Each blend is assigned arating number as shown below:

Water Repellency Water/IPA Rating Number Blend (% by volume) 0 100%water 1 90/10 water/IPA 2 80/20 water/IPA 3 70/30 water/IPA 4 60/40water/IPA 5 50/50 water/IPA 6 40/60 water/IPA 7 30/70 water/IPA 8 20/80water/IPA 9 10/90 water/IPA 10 100% IPA

In running the Water Repellency Test, a nonwoven web or film sample isplaced on a flat, horizontal surface. Five small drops of water or awater/IPA mixture are gently placed at points at least two inches aparton the sample. If, after observing for ten seconds at a 45° angle, fourof the five drops are visible as a sphere or a hemisphere, the nonwovenweb or film sample is deemed to pass the test. The reported waterrepellency rating corresponds to the highest numbered water or water/IPAmixture for which the nonwoven sample passes the described test.

It is desirable to have a water repellency rating of at least 4,preferably at least 6.

Test Method VI—Oil Repellency Test

Nonwoven web or film samples were evaluated for oil repellency using 3MOil Repellency Test III (February 1994), available from 3M Company, St.Paul, Minn. In this test, samples are challenged to penetration ordroplet spread by oil or oil mixtures of varying surface tensions. Oilsand oil mixtures are given a rating corresponding to the following:

Oil Repellency Oil Rating Number Composition 0 (fails Kaydol ™ mineraloil) 1 Kaydol ™ mineral oil 2 65/35 (vol) mineral oil/n-hexadecane 3n-hexadecane 4 n-tetradecane 5 n-dodecane 6 n-decane 7 n-octane 8n-heptane

The Oil Repellency Test is run in the same manner as is the WaterRepellency Test, with the reported oil repellency rating correspondingto the highest oil or oil mixture for which the nonwoven web or filmsample passes the test.

It is desirable to have an oil repellency rating of at least 1,preferably at least 3.

Preparation and Characterization of Antistats for Melting Point andThermal Decomposition

Antistat 1

Synthesis of Triethylammonium bis(perfluoroethanesulfonyl)imide, Et₃N⁺H⁻N(SO₂C₂F₅)₂

This compound was prepared essentially according to the method describedin U.S Pat. No. 5,874,616 (Howells, et al), Example 3, except that theprocedure was terminated once the methylene chloride solvent wasevaporated. The resulting product was characterized for melting point(T_(m)) according to Test Method I and for onset of thermaldecomposition (T_(d)) according to Test Method II. Results are shown inTable 1.

Antistat 2

Synthesis of Tetraethylammonium Trifluoromethanesulfonate, CF₃SO₃ ³¹⁺NEt₄

In a 2L flask, 300 g of CF₃SO₃H (FC-24) was charged. The acid wasneutralized by slow addition of about 800 g Et4NOH aqueous solution(35%) until the pH reached about 6. A white solid (560 g) was obtainedafter drying by rotary evaporation, then under high vacuum. The solidwas re-crystallized from chloroform-heptane to give 520 g pure product.This product was also characterized for melting point (T_(m)) accordingto Test Method I and for onset of thermal decomposition (T_(d))according to Test Method II. Results are shown in Table 1.

Antistat 3

Synthesis of Tetraethylammonium bis(trifluoromethanesulfonyl)imide,(CF₃SO₂)₂N⁻ ⁺NEt₄ in Water-CH₂Cl₂ Mixed Solvent

In a 1L flask, 50 g of (CF₃SO₂)₂N⁻ Li⁺ (HQ-115) was dissolved in 50 g ofdeionized water. The solution was combined with 89 g of 35% Et₄NOHaqueous solution under N₂. Solid precipitated during the addition, whichwas dissolved by the addition of 50 g CH₂Cl₂. The bottom organic layerwas isolated. The aqueous solution was extracted with another 50 g ofCH₂Cl₂. The combined organic solution was washed with water (2×25 mL),and volatiles were removed by rotary evaporation. Re-crystallization ofthe crude product from CH₃OH—H₂O gave 70 g of white solid after fullvacuum drying. The product was characterized for melting point (T_(m))according to Test Method I and for onset of thermal decomposition(T_(d)) according to Test Method II. Results are shown in Table 1.

Antistat 4

Synthesis of Tetrabutylammonium bis(trifluoromethanesulfonyl)imide,(C₄H₉)₄N⁺ ⁻N(SO₂CF₃)₂

This compound was prepared by reacting (C₄H₉)₄N⁺Br⁻ (Sigma-Aldrich,Milwaukee, Wis.) with approximately a 10% molar excess of Li⁺⁻N(SO₂CF₃)₂ (HQ-115) essentially according to the procedure described inExample 18 of U.S. Pat. No. 5,554,664 (Lamanna et al). The resultingproduct was characterized for melting point (T_(m)) according to TestMethod I and for onset of thermal decomposition (T_(d)) according toTest Method II. Results are shown in Table 1.

TABLE 1 Melting Point (T_(m)) and Onset of Thermal Decomposition (T_(d))Values T_(m) T_(d) Antistat Formula (° C.) (° C.) 1 Et₃N⁺H ⁻N(SO₂C₂F₅)₂−10 351 2 CF₃SO₃ ⁻ ⁺NEt₄ 133 371 3 (CF₃SO₂)₂N⁻ ⁺NEt₄ 8 426 4 (C₄H₉)₄N⁺⁻N(SO₂CF₃)₂ 93 401 23 (C₈H₁₇)₃N⁺(CH₃) Cl⁻ <28 177

The data in Table 1 shows that Antistats 1-4, which comprise weaklycoordinating fluoroorganic anions, exhibited much greater thermalstability than Antistat 23, which has the more strongly coordinatingchloride anion.

Antistat 5

Synthesis of 1-Hexadecylpyridinium Bis(perfluoroethanesulfonyl)imide,n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻N(SO₂C₂F₅)₂

This compound was prepared essentially according to the method ofAntistat 6, except that 85.1 g of Li⁺ ⁻N(SO₂C₂F₅)₂ (HQ-115) was employedas the anion precursor instead of Li⁺ ⁻OSO₂C₄F₉. The product wascharacterized for melting point (T_(m)) according to Test Method I andfor onset of thermal decomposition (T_(d)) according to Test Method II.Results are shown in Table 2.

Antistat 6

Synthesis of 1-Hexadecylpyridinium Perfluorobutanesulfonate,n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻OSO₂C₄F₉

Cetylpyridinium chloride monohydrate (75 g) was dissolved in 800 mlwater with gentle heating and magnetic stirring. To this solution wasadded 67.3 g of Li⁺⁻ OSO₂C₄F₉ (prepared by hydrolysis of C₄F₉SO₂F [PBSF]with LiOH) dissolved in 600 mL of water with stirring. The resultingproduct precipitated immediately and was isolated by suction filtration.The product was washed with copious amounts of water and then driedinitially by suction and then in vacuo at 10⁻² Torr, 40° C. The productwas characterized for melting point (T_(m)) according to Test Method Iand for onset of thermal decomposition (T_(d)) according to Test MethodII. Results are shown in Table 2.

Antistat 7

Synthesis of 1-Hexadecylpyridinium Perfluorooctanesulfonate,n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻OSO₂C₈F₁₇

This compound was prepared essentially according to the method ofAntistat 6, except that 111.3 g of Li⁺ ⁻OSO₂C₈F₁₇ (FC-94) was employedas the anion precursor. The resulting product was characterized formelting point (T_(m)) according to Test Method I and for onset ofthermal decomposition (T_(d)) according to Test Method II. Results areshown in Table 2.

Antistat 8

Synthesis of n-Butylpyridinium Bis(trifluoromethanesulfonyl)imide,n-C₄H₉-cyc-N⁺C₅H₅ ⁻N(SO₂CF₃)₂

A solution of 50 g Li⁺ ⁻N(SO₂CF₃)₂ (HQ-115) (287 g/mol, 0.174 mol) and100 ml DI water was prepared. Another solution of 30 g butylpyridiniumchloride (171.6 g/mol, 0.174) and 100 ml deionized water was prepared.The two solutions were added to a separatory funnel along with 200 mlmethylene chloride. The mixture was thoroughly shaken, and the phaseswere allowed to separate. The organic phase was isolated and washed with3×200 ml deionized water. The organic layer was then concentrated byreduced pressure distillation on a rotary evaporator. The resultingyellow oil was vacuum dried at 120 C. overnight to afford 70 g product(97% yield). The product was characterized for melting point (T_(m))according to Test Method I and for onset of thermal decomposition(T_(d)) according to Test Method II. Results are shown in Table 2.

Antistat 9

Synthesis of n-Butylpyridinium Perfluorobutanesulfonate,n-C₄H₉-cyc-N⁺C₅H₅ ⁻OSO₂C₄F₉

A solution of 20 g butylpyridinium chloride (171.6 g/mol, 0.116 mol) wasmade with 100 ml deionized water. A similar solution was prepared using35.7 g Li⁺⁻OSO₂C₄F₉ (prepared by hydrolysis of C₄F₉SO₂F [PBSF] withLiOH) (306 g/mol, 0.116 mol) and 100 ml water. The two solutions wereadded to a separatory funnel along with 200 ml methylene chloride. Themixture was thoroughly shaken, and the phases were allowed to separate.The organic phase was isolated and washed with 200 ml DI water. Themixture was slow to separate, consequently further washings were notdone. The organic layer was concentrated by reduced pressuredistillation on a rotary evaporator, and then dried under vacuum at 130°C. overnight. The resulting yellow oil weighed 44 g (87% yield) and wascharacterized for melting point (T_(m)) according to Test Method I andfor onset of thermal decomposition (T_(d)) according to Test Method II.Results are shown in Table 2.

TABLE 2 Melting Point (T_(m)) and Onset of Thermal Decomposition (T_(d))Values T_(m) T_(d) Antistat Formula (° C.) (° C.) 5 n-C₁₆H₃₃-cyc-N⁺C₅H₅⁻N(SO₂C₂F₅)₂ 34 396 6 n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻OSO₂C₄F₉ 95 357 7n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻OSC₂C₈F₁₇ 93 364 8 n-C₄H₉-cyc-N⁺C₅H₅ ⁻N(SO₂CF₃)₂ 33430 9 n-C₄H₉-cyc-N⁺C₅H₅ ⁻OSO₂C₄F₉ 63 391

Table 2 shows that the pyridinium cation-containing Antistats 5-9, whichcomprise weakly coordinating fluoroorganic anions, exhibited very goodthermal stability.

Antistat 10

Synthesis of 1,3-EthylmethylimidazoliumBis(trifluoromethanesulfonyl)imide, CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃⁻N(SO₂CF₃)₂

1,3-Ethylmethylimidazolium chloride (50.0 g) and LiN(SO₂CF₃)₂ (HQ-115)(102.8 g) were combined in 500 mL of water with magnetic stirring. Animmiscible light yellow oil of low viscosity separated as a lower liquidphase. The mixture was transferred to a separatory funnel, and 500 mL ofmethylene chloride was added. The mixture was shaken vigorously andallowed to phase separate. The lower organic phase was isolated andwashed with two additional 500 mL portions of water. The washedmethylene chloride phase was isolated, dried over anhydrous aluminumoxide beads, filtered by suction and vacuum stripped at 30-100° C.,20-10⁻³ Torr to remove all volatiles. A total of 112.2 g (84% yield) oflight yellow oil of high purity was obtained, which was identified asthe title compound by ¹H and ¹⁹F NMR. The product was also characterizedfor melting point (T_(m)) according to Test Method I and for onset ofthermal decomposition (T_(d)) according to Test Method II. Results areshown in Table 3.

Antistat 11

Synthesis of 1,3-Ethylmethylimidazolium Nonafluorobutanesulfonate,CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻OSO₂C₄F₉

1,3-Ethylmethylimidazolium chloride (49.1 g) and LiOSO₂C₄F₉ (107.6 g,prepared by hydrolysis of C₄F₉SO₂F with LiOH) were combined in 500 mL ofwater with magnetic stirring. A homogeneous aqueous solution was formed,which was transferred to a separatory funnel, combined with 500 mL ofCH₂Cl₂ and worked up essentially according to the procedure for Antistat10. After vacuum stripping all volatiles, a total of 65.0 g (47% yield)of light yellow oil of high purity was obtained, which was identified asthe title compound by ¹H and ¹⁹F NMR. The product was also characterizedfor melting point (T_(m)) according to Test Method I and for onset ofthermal decomposition (T_(d)) according to Test Method II. Results areshown in Table 3.

Antistat 12

Synthesis of 1,3-Ethylmethylimidazolium trifluoromethanesulfonate,CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻OSO₂CF₃

1,3-Ethylmethylimidazolium chloride (29 g, 0.199 mole) was dissolved in100 ml of water and added to solution of 50 g silver triflate (0.195mol) in 200 g water with stirring. The resulting silver chlorideprecipitate was removed by filtration, and the solids were washed with100 ml of deionized water. The filtrate was concentrated on a rotaryevaporator and further dried at 75° C. overnight to provide 47.5 g of alight green oil that was characterized by ¹H and ¹⁹F NMR. The productwas also characterized for melting point (T_(m)) according to TestMethod I and for onset of thermal decomposition (T_(d)) according toTest Method II. Results are shown in Table 3.

Antistat 13

Synthesis of 1,3-Ethylmethylimidazolium Tetrafluoroborate,CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ BF₄ ⁻

Separate solutions of 49.6 g AgBF4 (194.68 g/mol, 0.255 mol) in 200 mldistilled water, and 37.35 g 1,3-ethylmethylimidazolium chloride (146.62g/mol, 0.255 mol) in 200 ml distilled water were prepared. The twosolutions were mixed together, instantly forming a white precipitate.The precipitate was allowed to settle, followed by filtration through aD-frit. The filtrate was concentrated, but not to dryness, and allowedto stand at room temperature overnight. The next morning a blackprecipitate was observed to have fallen out of solution. The solutionwas passed through filter paper to removed the small amount of solid.The remaining water was removed by reduced pressure distillation on arotary evaporator. The remaining oil was dissolved in 200 mlacetonitrile. More insoluble black precipitate was formed and wasfiltered out of the solution. The resulting yellow filtrate wasconcentrated on the rotary evaporator, and the resulting oil was driedovernight under vacuum at 75 C. The isolated weight of product was 40 g(79% yield). The product was characterized for melting point (T_(m))according to Test Method I and for onset of thermal decomposition(T_(d)) according to Test Method II. Results are shown in Table 3.

Antistat 14

Synthesis of 1,3-Ethylmethylimidazolium Hexafluorophosphate,CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ PF₆ ⁻

A solution of 500 ml acetonitrile and 73.1 g 1,3-ethylmethylimidazoliumchloride (146.6 g/mol, 0.498 mol) was prepared in a 1L flask. Anothersolution of 250 ml acetonitrile and 81.1 g NH₄PF₆ (163 g/mol, 0.498 mol)was similarly prepared and added to the former solution. A whiteprecipitate instantly formed on mixing of the two solutions. The flaskwas chilled to near 0° C. for 1 hour followed by filtration through highpurity Celite™ filter agent using a D-frit. The solvent was removed fromthe filtrate by reduced pressure distillation on a rotary evaporator.The resulting ionic salt was dried under vacuum at 75 C. overnight. Theisolated weight of the ionic salt product was 114 g (89% yield). Theproduct was characterized for melting point (T_(m)) according to TestMethod I and for onset of thermal decomposition (T_(d)) according toTest Method II. Results are shown in Table 3.

TABLE 3 Melting point (T_(m)) and Onset of Thermal Decomposition (T_(d))Values T_(m) T_(d) Antistat Formula (° C.) (° C.) 10CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻N(SO₂CF₃)₂ −18 450 11CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻OSO₂C₄F₉ 18 410 12 CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃⁻OSO₂CF₃ −16 429 13 CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ BF₄ ⁻ 7 420 14CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ PF₆ ⁻ 70 490

The data of Table 3 show that the imidazolium cation-containingantistats, which comprise weakly coordinating fluoroorganic anions, allexhibited excellent thermal stability, with all T_(d) values greaterthan 400° C.

Antistat 15

Synthesis of 1-Dodecyl-2-ethyl-3-[2-hydroxyethyl]imidazoliniumToluenesulfonate, C₁₂H₂₅-cyc-[N⁺C₂H₄N(CH₂CH₂OH)C]C₂H₅ ⁻OSO₂C₆H₄CH₃

A 142.2 g sample of 2-ethyl-3-[2-hydroxyethyl]imidazoline (preparedessentially as described in U.S. Pat. No. 4,014,880) was combined with340 g of 1-dodecyl toluenesulfonate (prepared essentially as describedin Organic Synthesis, Collected Volume 3, p. 336 (1955) in a 1 literthree-neck round bottom flask and heated at a temperature of 75° C. withstirring for 4 hours. The resulting imidazolinium salt was transferredto a container for storage.

Antistat 16

Synthesis of Octyldimethyl-2-hydroxyethylammoniumbis(trifluoromethylsulfonyl)imide, C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻N(SO₂CF₃)₂

A 19.2 g sample of C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CH₃ (HTS 905A) wascombined with 15.7 g LiN(SO₂CF₃)₂ (HQ-115) in 120 mL of water. Afteragitating the mixture, a clear, immiscible oil separated as a lowerliquid phase. The mixture was transferred to a separatory funnel and 125mL of methylene chloride was added. The mixture was shaken vigorouslyand allowed to phase separate. The lower organic phase was isolated andwashed with two additional 125 mL portions of water. The washedmethylene chloride phase was isolated, dried over anhydrous aluminumoxide beads, filtered by suction and vacuum stripped at 30-100° C.,20-10⁻³ Torr to remove all volatiles. A colorless oil (22.6 g, 85%yield) of high purity was obtained, which was identified as the titlecompound by ¹H, ¹³C and ¹⁹F NMR. The product was also characterized formelting point (T_(m)) according to Test Method I and for onset ofthermal decomposition (T_(d)) according to Test Method II. Results areshown in Table 4.

Antistat 17

Synthesis of Octyldimethyl-2-hydroxyethylammoniumperfluorobutanesulfonate, C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂C₄F₉

A 118.5 g (0.399 mol) sample of C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CH₃ (HTS905A) was dissolved in about 250 ml of water and 123.9 g (0.399 mol) ofLiOSO₂C₄F₉ (prepared by hydrolysis of C₄F₉SO₂F [PBSF] with LiOH) wasdissolved in about 100 ml of water. The two solutions were added to aseparatory funnel and the mixture was shaken vigorously. Next 200 ml ofmethylene chloride was added to the funnel and the contents were shakenand allowed to phase separate. The lower methylene chloride layer waswashed twice with about 200 ml of water and concentrated on a rotaryevaporator at about 85° C. for about 45 minutes to yield an off-whitesolid product, which was characterized by ¹H and ¹³C nuclear magneticresonance spectroscopy (NMR). The product was also characterized formelting point (T_(m)) according to Test Method I and for onset ofthermal decomposition (T_(d)) according to Test Method II. Results areshown in Table 4.

Antistat 18

Synthesis of Octyldimethyl-2-hydroxyethylammoniumtrifluoromethanesulfonate, C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CF₃

Into 30 g of acetonitrile in a 125 ml Erlenmeyer flask was dissolvedwith heating 29.7 g (0.1 mole) HTS-905A (C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻O₃SCH₃)and then cooled in an ice bath for 10 minutes. In another 125 mlErlenmeyer flask was dissolved with heating 15.6 g (0.1 mole) lithiumtriflate into 30 ml of acetonitrile. Next, the lithium triflate solutionwas added over a period of about 1 minute to the stirred, cooledHTS-905A solution with generation of a white precipitate. About 2 ml ofacetonitrile was used to rinse the Erlenmeyer flask that held thelithium triflate solution, and this was also added to the HTS-905Asolution. The resulting reaction mixture was allowed to stir for about10 minutes and was then vacuum filtered through a pad of Celite™ filteragent on a 125 ml Buchner funnel with a C porosity frit. The reactionflask and Celite™ pad were washed with an additional 30 g of ice-coldacetonitrile. The filtrate was concentrated on a rotary evaporator atabout 50 mm Hg with a bath temperature of about 85° C. for about 45minutes to yield 24.5 g of a clear solid product, which wascharacterized by ¹H and ¹³C NMR. The product was also characterized formelting point (T_(m)) according to Test Method I and for onset ofthermal decomposition (T_(d)) according to Test Method II. Results areshown in Table 4.

Antistat 19

Synthesis of Octyldimethyl-2-hydroxyethylammoniumtris(trifluoromethanesulfonyl)methide, C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻C(SO₂CF₃)₃

A 20.0 g sample of C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CH₃ (HTS 905) was combinedwith 29.6 g HC(SO₂CF₃)₃ (prepared as described in Example 1 of U.S. Pat.No. 5,554,664 (Lamanna et al.) in 250 mL of water. After agitating theresulting mixture, a clear, viscous, pale yellow, immiscible oilseparated as a lower liquid phase. The mixture was transferred to aseparatory funnel, combined with 300 mL of methylene chloride, andworked up essentially according to the procedure Antistat 16. Aftervacuum stripping all volatiles, a total of 29.0 g (79% yield) of paleyellow oil product was obtained, which was identified as the titlecompound by ¹H and ¹⁹F NMR. Estimated purity from the NMR analysis wasgreater than 90 weight %, the major impurity being the corresponding⁻C(SO₂CF₃)₂(SO₂F) salt. The product was also characterized for meltingpoint (T_(m)) according to Test Method I and for onset of thermaldecomposition (T_(d)) according to Test Method II. Results are shown inTable 4.

Antistat 20

Synthesis of Trimethyl-2-acetoxyethylammoniumbis(trifluoromethylsulfonyl)imide, (CH₃)₃N⁺CH₂CH₂OC(O)CH₃ ⁻N(SO₂CF₃)₂

Acetylcholine chloride (98 g, Research Organics, Cleveland, Ohio) andLiN(SO₂CF₃)₂ (HQ-115) (165.8 g) were combined in 600 mL of water withmagnetic stirring. A viscous, immiscible oil separated as a lower liquidphase. The resulting mixture was worked up essentially as described forAntistat 16, except that the ionic liquid product was not completelymiscible with methylene chloride, forming 3 separate liquid phases inthe presence of water. The lower ionic liquid phase and the middleCH₂Cl₂ phase were both carried through the workup. After vacuumstripping all volatiles, a total of 179.1 g (77% yield) of colorless oilproduct of high purity was obtained, which was identified as the titlecompound by ¹H, ¹³C and ¹⁹F NMR. The product was also characterized formelting point (T_(m)) according to Test Method I and for onset ofthermal decomposition (T_(d)) according to Test Method II. Results areshown in Table 4.

Antistat 21

Synthesis of Trimethyl-2-hydroxyethylammoniumbis(perfluorobutanesulfonyl)imide, (CH₃)₃N⁺CH₂CH₂OH ⁻N(SO₂C₄F₉)₂

Choline chloride (37.34 g) and LiN(SO₂C₄F₉)₂ (142.7 g, preparedessentially according to Example 4 in U.S. Pat. No. 5,874,616 (Howellset al.) were combined in 400 mL of water with magnetic stirring. Aviscous, immiscible oil separated as a lower liquid phase. The mixturewas transferred to a separatory funnel, and 110 mL of diethyl ether wereadded. The mixture was shaken vigorously and allowed to phase separate.The lower organic phase was isolated and washed with two additional 400mL portions of water. The washed ether phase was isolated and vacuumstripped at 30-100° C., 20-10⁻³ Torr to remove all volatiles. Theresulting colorless oil product (155.3 g, 93% yield) of high purity wasobtained, which was identified as the title compound by ¹H, ¹³C and ¹⁹FNMR. The product was also characterized for melting point (T_(m))according to Test Method I and for onset of thermal decomposition(T_(d)) according to Test Method II. Results are shown in Table 4.

Antistat 22

Larostat™ HTS 905A, octyldimethylhydroxyethylammonium methanesulfonate(C₈H₁₇N⁺(CH₃)₂C₂H₄OH ⁻OSO₂CH₃) was also characterized for melting point(T_(m)) according to Test Method I and for onset of thermaldecomposition (T_(d)) according to Test Method II. Results are shown inTable 4.

TABLE 4 Melting Point (T_(m)) and Onset of Thermal Decomposition (T_(d))Values Anti- T_(m) T_(d) stat Formula (° C.) (° C.) 16C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻N(SO₂CF₃)₂ None 409 detected 17C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂C₄F₉ 147 374 18 C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH⁻OSO₂CF₃ −26 370 19 C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻C(SO₂CF₃)₃ None 387 detected20 (CH₃)₃N⁺CH₂CH₂OC(O)CH3 ⁻N(SO₂CF₃)₂ 24 361 21 (CH₃)₃N⁺CH₂CH₂OH⁻N(SO₂C₄F₉)₂ 32 402 22 C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CH₃ About 30 289

The results in Table 4 show that among antistats having the same cation,those containing weakly coordinating fluoroorganic anions (Antistats16-21) exhibited greatly increased thermal stability relative to that ofAntistat 22, which has a more strongly coordinating anion.

Antistat 23

Aliquat™ 336, methyltrioctylammonium chloride ((C₈H₁₇)₃N⁺(CH₃) Cl⁻), aliquid at room temperature, was characterized for onset of thermaldecomposition (T_(d)) according to Test Method II. Results are shown inTable 1.

Antistat 24

Synthesis of tetrabutylphosphonium perfluorobutanesulfonate, (C₄H₉)₄P⁺⁻OSO₂C₄F₉

This compound can be prepared as follows: Potassiumperfluorobutanesulfonate is prepared essentially as in Example 3 of U.S.Pat. No. 2,732,398 (Brice et al.), except that PBSF is substituted forCF₃(CF₂)₄SO₂F. The potassium ion is exchanged for a proton using an ionexchange column (Amberjet™ 1200 H, available from Sigma-Aldrich,Milwaukee, Wis.). The resulting perfluorobutanesulfonic acid is combinedwith an equal molar amount of tetrabutylphosphonium hydroxide (availablefrom Sigma-Aldrich, Milwaukee, Wis.) in an acid-base reaction, resultingin a high yield and high purity tetrabutylphosphoniumperfluorobutanesulfonate.

Preparation of Repellent Additives

Fluorochemical Repellent FR-1

Fluorochemical Repellent FR-1 (a fluorochemical oxazolidinone) wasprepared by reacting N-methylperfluorooctylsulfonamide withepichlorohydrin to form the fluorochemical chlorohydrin,C₈F₁₇SO₂N(Me)CH(OH)CH₂Cl, which was further reacted with octadecylisocyanate at a 1:1 molar ratio followed by ring closure usingessentially the same procedure as described in Scheme I of U.S. Pat. No.5,025,052 (Crater et al.).

Fluorochemical Repellent FR-2

Fluorochemical Repellent FR-2 (a fluorochemical ester) was prepared byesterifying MeFOSE alcohol with Empol™ 1008 dimer acid at a molar ratioof 2:1 using the following procedure. A 500 mL 2-necked round-bottomflask equipped with overhead condenser, thermometer and Dean-Stark trapwrapped with heat tape was charged with 57.8 g (0.190 eq) of Empol™ 1008dimer acid, 100 g (0.185 eq) of MeFOSE alcohol, 1 g of p-toluenesulfonicacid and 50 g of toluene. The resulting mixture was placed in an oilbath heated to 150° C. The degree of esterification was monitored bymeasuring the amount of water collected in the Dean-Stark trap and alsoby using gas chromatography to determine the amount of unreactedfluorochemical alcohol. After 18 hours of reaction, about 2.8 mL ofwater was collected and a negligible amount of fluorochemical alcoholremained, indicating a complete reaction. The reaction mixture was thencooled to 100° C. and was twice washed with 120 g aliquots of deionizedwater, the final water wash having a pH of 3. The final wash was removedfrom the flask by suction, and the reaction mixture was heated to 120°C. at an absolute pressure of about 90 torr to remove volatiles. Theresulting product, a brownish solid, was characterized as containing thedesired fluorochemical ester by ¹H and ¹³C NMR spectroscopy andthermogravimetric analysis.

Fluorochemical Repellent FR-3

Fluorochemical Repellent FR-3 (a fluorochemical ester) was prepared byesterifying MeFOSE alcohol with Pripol™ 1048 dimer/trimer acid at amolar ratio of 2:1 using essentially the same procedure as was used forpreparing Fluorochemical Repellent FR-2.

Fluorochemical Repellent FR4

Fluorochemical Repellent FR-4 (a fluorochemical ester) was prepared byesterifying MeFOSE alcohol with dodecanedioic acid at a molar ratio of2:1 using essentially the same procedure as was used for preparingFluorochemical Repellent FR-2.

Example 1

Fluorochemical Repellent FR-1 and HTS-905 (Antistat 22) were dry blendedwith a mixture of polybutylene PB0200 and polypropylene PP3505 400 meltflow resin (in a weight ratio of 1 part PB0200 to 10 parts PP3505) at0.85 and 1 weight % of the polypropylene resin, respectively. Themixture was extruded, on a 1.9 cm Brabender extruder with a 25.4 cm die,into blown microfibers with a diameter of less than about 10 microns(Wente, Van A., “superfine Thermoplastic fibers”, Industrial and Eng.Chemistry, Vol. 48, No. 8, 1956, pp. 1342-1345, and Naval ResearchLaboratory Report 111437, Apr. 15, 1954). The first extruder zone wasset at 265° C., and all other zones were set at 275° C. The die airtemperature was set at 277° C., and the melt temperature was recorded at279° C. The metering gear pump speed was set at 70 rpm. The die wasconfigured with an air gap setting of 0.763 mm and a set back of 0.69mm. With a collector distance of 30.5 cm, the take up speed was set todeliver a melt blown nonwoven formed from the microfibers with a basisweight of 50 grams/m². The resulting nonwoven samples were calendered ona 5% bond area embossing roll at 93.3° C. at 30.5 cm/min. and at 35.7Kg/lineal cm. The nonwoven samples were tested for oil and waterrepellency according to Test Methods V and VI. The nonwoven samples werealso conditioned at 50% relative humidity (23° C.) and tested for staticcharge dissipation according to Test Method III. Results are shown inTable 5.

Comparative Example C1

Nonwoven samples were made and tested essentially as in Example 1,except that no HTS-905 was used. The results are shown in Table 5.

Comparative Example C2

Nonwoven samples were made and tested essentially as in Example 1,except that no repellent was used, and the level of HTS-905 was 0.5weight % of the polypropylene resin. The results are shown in Table 5.

TABLE 5 Repellency and Static Charge Dissipation Properties ofPolypropylene Melt-Blown Nonwovens Repel- Repel- Static lent Antistatlency Decay Example No. (Wt %) (Wt %) O W (sec) 1 FR-1 Antistat 22 6 100.07 (0.85%) (1%) C1 FR-1 None 6 10 >100.0 (0.85%) C2 None Antistat 22 0 3 0.01 (1%) O = oil W = water

The results in Table 5 show that the combination of repellent and ionicantistat compound in a thermoplastic polymer provided excellent staticcharge dissipation and excellent repellency properties.

Examples 2-6 and Comparative Example C3

Fluorochemical Repellent FR-1 and Antistat 15C₁₂H₂₅-cyc-[N⁺C₂H₄N(CH₂CH₂OH)C]C₂H₅ ⁻OSO₂C₆H₄CH₃) were dry blended withPP3505. FR-1 was used at 1 weight % based on the weight of PP3505, andAntistat 15 was used at 0.5, 0.6, 0.7, 0.8, and 1 weight %, also basedon the weight of PP3505. Nonwoven samples were made and testedessentially as in Example 1. For comparison purposes, nonwoven sampleswere made and tested essentially as in Example 1 without repellent orantistat (Comparative Example C3). The results are shown in Table 6.

Example 7

Fluorochemical Repellent FR-1 (1 weight %) and Antistat 15 (1 weight %)were dry blended with a mixture of PP3505 (80 weight %) and PB8340 (20weight %). Nonwoven samples were made and tested essentially as inExample 1, and the results are shown in Table 6.

TABLE 6 Repellency and Static Charge Dissipation Properties ofPolypropylene Melt-Blown Nonwovens Static Repellent FR-1 Antistat 15Repellency Decay Example No. (weight %) (weight %) Oil Water (sec) C3 00 0 2 WNC¹ 2 1.0 0.5 3 8 0.15 3 1.0 0.6 3 8 0.11 4 1.0 0.7 2 8 0.06 51.0 0.8 2 8 0.09 6 1.0 1.0 2 8 0.04 7 1.0 1.0 4 9 0.05 ¹Will not acceptcharge, therefore not antistatic.

The results in Table 6 show that a combination of a fluorochemicaloxazolidinone and Antistat 15 (imidazolinium toluenesulfonate ionicantistat) provided both repellency and good static charge dissipationproperties in polypropylene, and that these properties were furtherenhanced with added polybutylene.

Example 8

Fluorochemical Repellent FR-1 (0.85 weight %) and antistat HTS-904 (1weight %) were dry blended with PP3505. Nonwoven samples were made fromthis blend and tested essentially as in Example 1. The results are shownin Table 7.

Example 9

Fluorochemical Repellent FR-1 (0.85 weight %) and antistat HTS-904 (1weight %) were dry blended with a mixture of PP3503 (85 weight %) andPB8340 (15 weight %). Nonwoven samples were made from this blend andtested essentially as in Example 1. The results are shown in Table 7.

TABLE 7 Repellency and Static Charge Dissipation Properties ofPolypropylene Melt-Blown Nonwovens Repel- Repel- Static Example PB8340lent Antistat lency Decay No. (Wt %) (wt %) (Wt %) O W (sec) 8 0 FR-1HTS-904 2 9 0.01 (0.85%) (1%) 9 15 FR-1 HTS-904 6 10 0.05 (0.85%) (1%) O= oil W = water

The results in Table 7 show that the addition of polybutylenesignificantly increased the repellency of a polypropylene nonwovencontaining a combination of a fluorochemical repellent and an antistat,without loss of excellent antistatic properties.

Comparative Examples C4-C6

Nonwoven samples containing 0 or 1.0 weight % Fluorochemical RepellentFR-1 and 0, 1.0, or 1.25 weight % Anstex™ SA-300 nonionic antistat wereprepared and tested essentially as in Example 1. The results are shownin Table 8.

TABLE 8 Repellency and Static Charge Dissipation Properties ofPolypropylene Melt-Blown Nonwovens Antistat Static Repellent FR-1 SA-300Repellency Decay Example No. (wt. %) (wt. %) Oil Water (sec) C3 0 1.0 02 14.9 C4 1.0 0.0 4 9 WNC¹ C5 1.0 1.25 4 8 WNC¹ ¹Will not accept charge,therefore not antistatic.

The results in Table 8 show that a loss of antistatic properties wasobtained when a nonionic antistat was used in combination with arepellent.

Examples 10-19 and Comparative Examples C7-C17

Antistats 16-19 and 22 along with 1 or 1.25 weight % FluorochemicalRepellent FR-1, FR-2, FR-3, or FR-4 were incorporated into polypropylenemelt blown fibers, which were processed into nonwoven fabrics accordingto the melt-blown extrusion procedure described in U.S. Pat. No.5,300,357 (Gardiner), column 10, the description of which isincorporated herein by reference. For comparison, polypropylene meltblown fibers without repellent or antistat, and with an Antistat butwithout a repellent were made and formed into nonwoven fabrics byessentially the same process. For additional comparison, polypropylenemelt blown fibers with only Fluorochemical Repellents FR-1, FR-2, FR-3,or FR-4 were made and processed into nonwoven fabrics by essentially thesame process. The extruder used was a Brabender 42 mm conical twin screwextruder, with maximum extrusion temperature of 270-280° C. and distanceto the collector of 12 inches (30 cm).

Antistat, Fluorochemical Repellent, and Escorene ™ PP3505 polypropylenewere mixed by blending in a paperboard container using a mixer headaffixed to a hand drill for about one minute until a visuallyhomogeneous mixture is obtained. The Antistat and FluorochemicalRepellent were dispersed in the molten polypropylene by mixing in themelt extrusion apparatus just prior to melt blowing. Except as noted,the weight percent of the compound in the polypropylene was about 1%.

The process condition for each mixture was the same, including the meltblowing die construction used to blow the microfiber web, the basisweight of the web (50±5 g/m²) and the diameter of the microfibers (5-18micrometers). Unless otherwise stated, the extrusion temperature was270-280° C., the primary air temperature was 270° C., the pressure was124 kPa (18 psi), with a 0.076 cm air gap width, and the polymerthroughput rate was about 180 g/hr/cm.

The resulting melt blown polypropylene fabrics were evaluated forantistatic performance, oil repellency, and water repellency using TestMethods III, V, and VI. The results are shown in Tables 9 and 10.

TABLE 9 Static Charge Dissipation, Oil Repellency, and Water Repellencyof Escorene ™ PP3505 Polypropylene Nonwovens Charge (Kvolts) StaticDecay (sec) Repellent Antistat Repellency 10% 25% 50% 10% 25% 50% Ex.No. (Wt %) (Wt %) O W RH RH RH RH RH RH C6 None None 0 2 4.3 5+ 5+ 60+60 60 1.7 1.7 >10 >10 5 5 >10 >10 C7 FR-1 1% None 1 8 WNC WNC WNC WNCWNC WNC C8 FR-2 1% None 0 7 NR NR NR NR NR NR C9 FR-3 1.25% None 0 7 NRNR −.5 NR NR >10 C10 FR-4 1% None 1 7 NR NR −.75 NR NR >10 RH = relativehumidity WNC = will not accept charge (therefore not antistatic) NR =not run O = oil W = water

The results in Table 9 show that polypropylene nonwoven alone lacked oiland water repellency and antistatic properties, and that the addition offluorochemical repellents significantly increased repellency,particularly the water repellency of polypropylene, but made nocontribution to improvement of antistatic properties.

TABLE 10 Static Charge Dissipation, Oil Repellency, and Water Repellencyof Escorene ™ PP3505 Polypropylene Nonwovens Repel- Repel- Charge(Kvolts) Static Decay (sec) Ex. lent Antistat lency 10% 25% 50% 10% 25%50% No. (Wt %) (Wt %) O W RH RH RH RH RH RH C12 None Antistat 22 0 2 5+3.4 5+ 0.86 0.14 0.03 (1%) 10 FR-1 Antistat 22 2 9 5 5 5 0.6 0.3 0.03(1%) (1%) 11 FR-2 Antistat 22 1 7 5 5 4 0.7 0.3 0.05 (1%) (1%) 12 FR-4Antistat 22 1 5 5 5 4 1.3 1.1 0.4 (1%) (1%) C13 None Antistat 16 0 2 5+5+ 5+ 0.14 0.19 0.63 (1%) 13 FR-1 Antistat 16 1.5 9 5 5 5 0.5 0.2 0.2(1%) (1%) 14 FR-3 Antistat 16 1 7 4 4.7 4.5 0.1 0.09 0.1 (1.25%) (1%) 15FR-4 Antistat 16 0 5 4 4.5 4.7 0.6 0.2 2.8 (1%) (1%) C14 None Antistat16 0 2 NR 5 5 NR >10 0.95 (0.5%) 16 FR-1 Antistat 16 1 7 5 5 5 0.5 0.20.2 (1%) (0.5%) C15 None Antistat 17 0.5 2 5 5 5 0.90 0.02 0.02 (1%) 17FR-1 Antistat 17 1 8 4.2 4.6 5 8.8 7.3 1.4 (1%) (1%) C16 None Antistat18 0 2 5 5 5 4.17 0.09 0.03 (1%) 18 FR-1 Antistat 18 2 9 5 5 5 0.2 0.10.04 (1%) (1%) C17 None Antistat 19 0 2 NR NR 5 NR NR >10 (1%) 19 FR-1Antistat 19 2 9 5 5 5 0.3 0.1 0.2 (1%) (1%) RH = relative humidity NR =not run O = oil W = water

The results in Table 10 together with those in Table 9 show that thepresence of a combination of a fluorochemical repellent and anoctyldimethyl-2-hydroxyethylammonium antistat produced excellentantistatic properties with repellency essentially the same as whenrepellent was used alone, and, in some cases, improved the antistaticproperties compared with those found when the antistat was used alone.

Examples 20-26 and Comparative Examples C18-C23

Antistats 1-4, 20, and 21 alone and in combination with 1 or 1.25 weight% Fluorochemical Repellent FR-1 or FR-3 were incorporated intopolypropylene melt blown fibers and processed into nonwoven fabricsessentially as in Examples 10-19 and Comparative Examples C12-C17. Theresulting melt blown polypropylene fabrics were evaluated for antistaticperformance, oil repellency, and water repellency using Test MethodsIII, V, and VI. The results are shown in Table 11.

TABLE 11 Static Charge Dissipation, Oil Repellency, and Water Repellencyof Escorene ™ PP3505 Polypropylene Nonwovens Repel- Repel- Charge(Kvolts) Static Decay (sec) Ex. lent Antistat lency 10% 25% 50% 10% 25%50% No. (wt %) (wt %) O W RH RH RH RH RH RH C18 None Antistat 20 0 2 NR5+ 5+ NR >60 >60 (1%) 20 FR-1 (1%) Antistat 20 1 8 5+ 5+ 5+ 0.01 0.030.9 (1%) 21 FR-3 Antistat 20 1 8 NR 5+ 4.4 NR 0.02 0.06 (1.25%) (1%) C19None Antistat 21 0 2 NR 4.8 5+ NR 56 >60 (1%) 22 FR-1 (1%) Antistat 211.5 9 NR 5+ 5+ NR >60 0.9 (1%) C20 None Antistat 1 0 2 5 5 5 0.03 0.030.02 (1%) 23 FR-1 (1%) Antistat 1 1 9 NR 2.5 2.5 NR >10 0.01 (1%) C21None Antistat 2 0 2 NR NR 5 NR NR >10 (1%) 24 FR-1 (1%) Antistat 2 2 9NR NR −1.5 NR NR >10 (1%) C22 None Antistat 3 0 2 NR NR 5 NR NR >10 (1%)25 FR-1 (1%) Antistat 3 2 9 NR 0.7 1.5 NR >10 0.01 (1%) C23 NoneAntistat 4 0 2 NR 3.7 3.6 NR 60 60 (1%) 26 FR-1 (1%) Antistat 4 1 8 NR 44.2 NR 2.8 11 (1%) RH = relative humidity NR = not run O = oil W = water

The results in Table 11 together with those in Table 9 show that thecombination of fluorochemical repellent and an alkyl ammonium anti statprovided essentially the same or better repellency compared with therepellency obtained when the repellent was used alone. Furthermore, thecombination of fluorochemical repellent and antistat often providedsignificantly improved antistatic properties.

Examples 27-34 and Comparative Examples C24-C28

Antistats 5-9 alone and in combination with 1 or 1.25 weight %Fluorochemical Repellent FR-1 or FR-3 were incorporated intopolypropylene melt blown fibers and processed into nonwoven fabricsessentially as in Examples 10-19 and Comparative Examples C12-C17. Theresulting melt blown polypropylene fabrics were evaluated for antistaticperformance, oil repellency, and water repellency using Test MethodsIII, V, and VI. The results are shown in Table 12.

TABLE 12 Static Charge Dissipation, Oil Repellency, and Water Repellencyof Escorene ™ PP3505 Polypropylene Nonwovens Repel- Repel- Charge(Kvolts) Decay Rate (sec) Ex. lent Antistat lency 10% 25% 50% 10% 25%50% No. (wt %) (wt %) O W RH RH RH RH RH RH C24 None Antistat 5 (1%) 0 24.8 4.7 5+ 34 8.9 45 27 FR-1 Antistat 5 (1%) 1 6 5+ 5+ 5+ 1.3 0.7 1.1(1%) 28 FR-3 Antistat 5 (1%) 0.5 6 5+ 5+ 5+ 0.4 1.3 0.6 (1.25%) C25 NoneAntistat 6 (1%) 0 2 NR 5+ 5+ NR 56 1.01 29 FR-1 Antistat 6 (1%) 1 7 NR2.7 4.7 NR 5 21 (1%) 30 FR-3 Antistat 6 (1%) 1 6 NR 1.3 4.2 NR 0.01 33(1.25%) C26 None Antistat 7 (1%) 0 2 NR 3.6 5+ NR >60 3.98 31 FR-1Antistat 7 (1%) 1 7 NR 4.3 5+ NR >60 9.9 (1%) 32 FR-3 Antistat 7 (1%) 16 NR 4.2 5+ NR 36 9.9 (1.25%) C27 None Antistat 8 (1%) 0 2 NR 5+ 4.3 NR49 0.06 33 FR-1 Antistat 8 (1%) 1.5 9 NR 5+ 5+ NR >60 1.5 (1%) C28 NoneAntistat 9 (1%) 0 2 NR 5+ 5+ NR >60 0.46 34 FR-1 Antistat 9 (1%) 2 10 NR5+ 5+ NR >60 0.5 (1%) RH = relative humidity NR = not run O = oil W =water

The results in Table 12 together with those in Table 9 show that thecombination of fluorochemical repellent and alkyl pyridinium antistatprovided essentially the same or better repellency compared with therepellency found when the repellent was used alone. Furthermore, thecombination of repellent and antistatic compound provided significantlyimproved antistatic properties in some instances.

Examples 35-38 and Comparative Examples C29-C32

Antistats 10-14 alone and in combination with 1 weight % FluorochemicalRepellent FR-1 were incorporated into polypropylene melt blown fibersand processed into nonwoven fabrics essentially as in Examples 10-19 andComparative Examples C12-C17. The resulting melt blown polypropylenefabrics were evaluated for antistatic performance, oil repellency, andwater repellency using Test Methods III, V, and VI. The results areshown in Table 13.

TABLE 13 Static Charge Dissipation, Oil Repellency, and Water Repellencyof Escorene ™ PP3505 Polypropylene Nonwovens Repel- Repel- Charge(Kvolts) Decay Rate (sec) Ex. lent Antistat lency 10% 25% 50% 10% 25%50% No. (wt %) (wt %) O W RH RH RH RH RH RH C29 None Antistat 10 0 2 4.13.9 3.4 60+ 0.01 53 (1%) 35 FR-1 Antistat 10 2 8 4.7 5 5+ 0.01 0.02 0.03(1%) (1%) C30 None Antistat 11 0 2 5+ 5+ 5+ 0.02 20 0.03 (1%) 36 FR-1Antistat 11 1.5 8 5+ 5+ 5+ 0.7 0.04 0.03 (1%) (1%) C31 None Antistat 130 2 4.5 4.9 4.2 >60 >60 >60 (1%) 37 FR-1 Antistat 13 1 8 4.5 5+ 5+ 0.100.02 0.10 (1%) (1%) C32 None Antistat 14 0 2 NR 3.8 4.4 NR >60 >60 (1%)38 FR-1 Antistat 14 1 8 4 3.7 3.6 1.8 0.02 0.01 (1%) (1%) RH = relativehumidity NR = not run O = oil W = water

The results in Table 13 together with those in Table 9 show that thecombination of repellent and imidazolium antistat provided essentiallythe same or better repellency compared with the repellency found whenthe repellent was used alone. Furthermore, the combination of repellentand antistat provided significantly improved antistatic properties.

Example 39 and Comparative Example C33

Antistat 24 alone and in combination with 1 weight % FluorochemicalRepellent FR-1 was incorporated into polypropylene melt blown fibers andprocessed into nonwoven fabrics essentially as in Examples 10-19 andComparative Examples C12-C17. The resulting melt blown polypropylenefabrics were evaluated for antistatic performance, oil repellency, andwater repellency using Test Methods III, V, and VI. The results areshown in Table 14.

TABLE 14 Static Charge Dissipation, Oil Repellency, and Water Repellencyof Escorene ™ PP3505 Polypropylene Nonwovens Charge (Kvolts) Decay Rate(sec) Repellent Antistat Repellency 10% 25% 50% 10% 25% 50% Ex. No. (wt%) (wt %) O W RH RH RH RH RH RH C33 None Antistat 24 0 2 NR 5+ 5+ NR 2512 (1%) 39 FR-1 Antistat 24 3 9 5 4.9 4.3 0.5 0.4 0.6 (1%) (1%) O = oilW = water RH = relative humidity NR = not run

The results in Table 14 together with those in Table 9 show that thecombination of repellent and phosphonium antistat provided essentiallythe same or better repellency compared with the repellency found whenthe repellent was used alone. Furthermore, the combination of repellentand antistat provided significantly improved antistatic properties.

Example 40 and Comparative Example C34

Lithium perfluorobutanesulfonate alone and in combination with 1 weight% Fluorochemical Repellent FR-1 was incorporated into polypropylene meltblown fibers and processed into nonwoven fabrics essentially as inExamples 10-19 and Comparative Examples C12-C17. The resulting meltblown polypropylene fabrics were evaluated for antistatic performance,oil repellency, and water repellency using Test Methods III, V, and VI.The results are shown in Table 15.

TABLE 15 Static Charge Dissipation, Oil Repellency, and Water Repellencyof Escorene ™ PP3505 Polypropylene Nonwoven Repel- Charge (Kvolts) DecayRate (sec) Ex. Repellent lency 10% 25% 50% 10% 25% 50% No. (Wt %)Antistat (Wt %) O W RH RH RH RH RH RH C34 None Li+ —OSO₂C₄F₉ 0 2 NR NR 5NR NR 0 40 FR-1 Li+ —OSO₂C₄F₉ 1 6 NR NR 5 NR NR 0.03 O = oil W = waterRH = relative humidity NR = not run

The results in Table 15 together with those in Table 9 show that thecombination of repellent and lithium perfluorobutanesulfonate antistatprovided essentially the same repellency as that found when therepellent was used alone. Furthermore, the combination of repellent andantistat provided essentially the same antistatic properties as thatfound when the antistat was used alone.

Comparative Examples C35-C43

Aluminum stearate, lithium stearate, and glycerol monostearate incombination with 1 weight % Fluorochemical Repellent FR-1, FR-2, or FR-4was incorporated into polypropylene melt blown fibers and processed intononwoven fabrics essentially as in Examples 10-19 and ComparativeExamples C12-C17. The resulting melt blown polypropylene fabrics wereevaluated for antistatic performance, oil repellency, and waterrepellency using Test Methods III, V, and VI. The results are shown inTable 16.

TABLE 16 Static Charge Dissipation, Oil Repellency, and Water Repellencyof Escorene ™ PP3505 Polypropylene Nonwoven Repel- Charge (Kvolts) DecayRate (sec) Ex. Repellent lency 25% 50% 25% 50% No. (Wt %) Antistat (Wt%) O W RH RH RH RH C35 FR-1 (1%) AlOCO(CH₂)₁₆CH₃ 0 9 NR −1 NR >10 (1%)C36 FR-1 (1%) LiOCO(CH₂)₁₆CH₃ 1 9 NR 2.4 NR >10 (1%) C37 FR-1 (1%)HOCH2CH(OH)CH2O— 1 9 1.2 0.9 0 >10 CO(CH₂)₁₆CH₃ (1%) C38 FR-2 (1%)AlOCO(CH₂)₁₆CH₃ 2 8 NR 2 NR >10 (1%) C39 FR-2 (1%) LiOCO(CH₂)₁₆CH₃ 1 8NR −0.5 NR >10 (1%) C40 FR-2 (1%) HOCH2CH(OH)CH2O— 0 5 NR 2 NR >10CO(CH₂)₁₆CH₃ (1%) C41 FR-4 (1%) AlOCO(CH₂)₁₆CH₃ 1 9 NR 0.5 NR >10 (1%)C42 FR-4 (1%) LiOCO(CH₂)₁₆CH₃ 2 6 NR −0.9 NR >10 (1%) C43 FR-4 (1%)HOCH2CH(OH)CH2O— 2 8 NR 2.2 NR >10 CO(CH₂)₁₆CH₃ (1%) RH = relativehumidity NR = not run O = oil W = water

The results in Table 16 show that neither the nonionic antistaticcompounds nor the ionic antistatic compounds (that lack an anion forwhich the conjugate acid is a strong acid) provided antistaticproperties in combination with fluorochemical repellents.

Example 41 and Comparative Examples C44-C46

Antistat 16, C₈H₁₇N⁺(CH₃)₂C₂H₄OH ⁻N(SO₂CF₃)₂ (2 weight %) andFluorochemical Repellent FR-1 (2 weight %) were incorporated intoMORTHANE™ PS440-200 urethane melt blown fibers, which were made andprocessed into a nonwoven fabric essentially as described in Examples10-19, except that the extrusion temperature was 230° C. Forcomparisons, MORTHANE™ PS440-200 urethane melt blown fibers withoutantistat or repellent, with Antistat 16 (2 weight %) alone, and withFluorochemical Repellent FR-1 (2 weight %) alone were made and processedinto nonwoven fabrics essentially as described in Comparative ExamplesC7-C 17. The resulting fabrics were tested for antistatic performance,oil repellency, and water repellency, using Test Methods III, V, and VI.The results are shown in Table 17.

TABLE 17 Static Charge Dissipation, Oil Repellency, and Water Repellencyof Melt Blown MORTHANE ™ PS440-200 Urethane Nonwoven Fabrics Repel-Charge (Kvolts) Decay Rate (sec) Ex. Repellent lency 10% 25% 50% 10% 25%50% No. (Wt %) Antistat (Wt %) O W RH RH RH RH RH RH C44 None None 0 2NR 5 5 NR >60 >60 C45 None Antistat 16 (2%) 0 2 5 5 5 0.09 0.08 0.08 C46FR-1 (2%) None 6 4 5 5 5 4.20 3.34 2.4 41 FR-1 (2%) Antistat 16 (2%) 6 75 5 5 0.08 0.06 0.07 RH = relative humidity NR = not run O = oil W =water

The results in Table 17 show that the combination of fluorochemicalrepellent and ionic antistat provided both very good repellency and goodantistatic properties in polyurethane nonwoven fabric.

Example 42 and Comparative Example C47-49

Antistat 16 (1 weight %) and Fluorochemical Repellent FR-1 (1 weight %)were incorporated into ASPUN™ 6806 poly(ethylene/octene) melt blownfibers, which were made and processed into a nonwoven fabric essentiallyas described in Examples 10-19, except that the extrusion temperaturewas 240° C. For comparisons, ASPUN™ 6806 melt blown fibers without anyantistat or repellent, with Antistat 16 (1 weight %) alone, and withFluorochemical Repellent FR-1 (1 weight %) alone were made and processedinto nonwoven fabrics essentially as described in Comparative ExamplesC7-C17. The resulting fabrics were tested for antistatic performance,oil repellency, and water repellency, using Test Methods III, V, and VI.The results are shown in Table 18.

TABLE 18 Static Charge Dissipation, Oil Repellency, and Water Repellencyof Melt Blown ASPUN ™ 6806 Poly(ethylene/octene) Nonwoven Fabrics Repel-Charge (Kvolts) Decay Rate (sec) Ex. Repellent lency 10% 25% 50% 10% 25%50% No. (Wt %) Antistat (Wt %) O W RH RH RH RH RH RH C47 None None 0 2NR NR 3 NR NR >60 C48 None Antistat 16 (1%) 0 2 5 5 5 0.07 0.08 0.07 C49FR-1 (1%) None 3 9 NR 1.7 3 NR 0.00 7.68 42 FR-1 (1%) Antistat 16 (1%) 67 5 5 5 0.02 0.01 0.01 RH = relative humidity NR = not run O = oil W =water

The results in Table 18 show that the combination of fluorochemicalrepellent and ionic antistat provided both very good repellency andexcellent antistatic properties in poly(ethylene/octene) nonwovenfabric.

Examples 43-45 and Comparative Example 50

Polypropylene films containing tetrabutylphosphoniumperfluorobutanesulfonate (Antistat 24) and Fluorochemical RepellentFR-1, FR-3, or FR-4 were prepared and evaluated for repellency andantistatic performance. For comparison, a polypropylene film withoutantistat or repellent was essentially identically prepared andevaluated. The melt-blown nonwoven fabrics of Example 39, andComparative Example 7, as well as nonwoven fabrics made essentiallyidentically to Example 39 but with FR-3 and FR-4 substituted for FR-1were pressed into films as follows: About 3.4 g of the folded melt-blownfabric was placed on a steel plate within the perimeter of an 11.2 cm by17.1 cm by 0.177 mm thick shim and covered with another steel plate.This assembly was then placed on a platen press heated to 200° C., withthe platens nearly touching, for about 30 seconds to pre-melt the fabricand allow for escape of air before pressing. Next, the construction wasplaced under 0.91 metric ton of pressure for about one minute. Theassembly was removed from the press and allowed to cool for about 30seconds between two unheated platens. The formed film was then removedfrom the shim and steel plates.

The resulting films were evaluated for antistatic performance, oilrepellency, and water repellency using Test Methods III, V, and VI. Theresults are shown in Table 19.

TABLE 19 Static Charge Dissipation, Oil Repellency, and Water Repellencyof Escorene ™ PP3505 Polypropylene Films Repel- Charge (Kvolts) DecayRate (sec) Ex. Repellent lency 10% 25% 50% 10% 25% 50% No. (Wt %)Antistat (Wt %) O W RH RH RH RH RH RH C50 None None 0 4 NR NR 1.5 NRNR >10 43 FR-1 (1%) Antistat 24 (1%) 2 10 NR 5 5 NR >10 1.3 44 FR-3 (1%)Antistat 24 (1%) 1 8 5 5 4.3 >10 2.1 0.7 45 FR-4 (1%) Antistat 24 (1%) 14 5 5 4.2 4.4 1.6 0.02 RH = relative humidity NR = not run O = oil W =water

The results in Table 19 show that the combination of fluorochemicalrepellent and phosphonium antistat provided both good repellency andgood antistatic properties in polypropylene films.

Examples 46-49 and Comparative Examples C51-56

A polypropylene nonwoven fabric, having a basis weight of 220 grams/m²,was made essentially as Comparative Example 7, but using Montell™ H442PP(polypropylene) with the collector speed adjusted for this basis weight.The resulting fabric was tested for oil repellency, water repellency,and antistatic performance (Test Methods V, VI, and III) before andafter topical treatment with a repellent, various ionic antistats, andcombinations of the repellent and antistats. Pad bath solutions (500grams) made up of 80 weight % water and 20 weight % isopropanol (IPA)without and with 0.366 weight % repellent (9.15 grams of 20 weight %solids FC-808 diluted to 500 grams with the 80/20 water IPA), with 0.366weight % antistat, and with combinations of 0.366 weight % repellent and0.366 weight % antistat were prepared. A weighed (4-6 grams) piece ofnonwoven fabric was dipped in each pad bath and passed between two 12.7cm rubber rolls at a pressure of 0.41 MPa and a speed of 7.6 m/min. Thewet fabric was weighed and then dried in a forced air oven at 149° C.for five minutes. The target amount of repellent and antistat applied tothe fabric was 0.55 weight %. The actual amount ranged from 0.51 to0.64%. Repellency and antistatic properties of the topically treatednonwoven fabric are shown in Table 20.

TABLE 20 Static Charge Dissipation, Oil Repellency, and Water Repellencyof Topically Treated Polypropylene Nonwovens Repel- Charge (Kvolts)Decay Rate (sec) Ex. Repellent lency 10% 25% 50% 10% 25% 50% No. (Wt %)Antistat (Wt %) O W RH RH RH RH RH RH C51 None None 0 2 5 4.32.2 >10 >10 >10 C52 FC-808 (0.54%) None 6 10 5 NR 5 >10 NR 2.1 C53 NoneAntistat 22 (0.56%) 0 1 5 5 5 1.1 1.3 0.15 46 FC-808 (0.51%) Antistat 22(0.51%) 7 10 5 5 5 .02 .03 .01 C54 None Antistat 23 (0.55%) 0 0 5 5 50.01 0.04 0.01 47 FC-808 Antistat 23 6 10 5 5 5 0.01 0.07 0.01(0.53-0.64%) (0.53-0.64%) C55 None Sodium p- 0 2 NR NR 3.5 NR NR >10Toluenesulfonate (0.55%) 48 FC-808 (0.51%) Sodium p- 6 10 5 5 5 1.5 2.00.1 Toluenesulfonate (0.51%) C56 None Antistat 16 (0.52%) 0 1 5 5 5 2.12.9 1.4 49 FC-808 Antistat 16 8 10 5 5 5 0.01 0.01 0.01 (0.51-0.53%)(0.51-0.53%) RH = relative humidity NR = not run O = oil W = water

The results in Table 20 show that surprising and excellent antistaticand repellency properties were obtained by topically treating a nonwovenwith a composition comprising an antistat and a fluorochemicalrepellent.

Example 50 and Comparative Examples C57-C59

A thermoset epoxy coating was prepared by mixing 5 grams part A (aminepart) and 6 grams part B (epoxy part) of Scotchweld™ 1838-iB/ATranslucent Epoxy Adhesive (available from 3M, St. Paul Minn.). Themixture was poured at the top of a 25.5 cm by 15.5 cm by 0.102 mm thickprimed polyester terephthalate film and then drawn over the film using aNo. 12 wire wound (Meyer) bar. The resulting coating was cured at 65° C.for one hour in a forced air oven. The above procedure was repeatedusing separate 5 gram quantities of part A containing 0.33 gram1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (Antistat10), 0.33 gram Fluorochemical Repellent FR-3, and a combination of 0.33gram 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and0.33 gram Fluorochemical Repellent FR-3, respectively. The curedcoatings were tested for antistatic performance, oil repellency, andwater repellency using Test Methods III, V, and VI. The results areshown in Table 21.

TABLE 21 Static Charge Dissipation, Oil Repellency, and Water Repellencyof Thermoset Epoxy Coatings Decay Charge Rate Repel- (Kvolts) (sec) Ex.Repellent lency 50% 50% No. (Wt %) Antistat (Wt %) O W RH RH C57 NoneNone 1 6 5 >60 C58 None Antistat 10 (2.9%) 1 3 5 24 C59 FR-3 (2.9%) None8 10 5 >60 50 FR-3 (2.9%) Antistat 10 (2.9%) 8 10 5 9.6 RH = relativehumidity O = oil W = water

The results in Table 21 show that high oil and water repellency and someimprovement in antistatic properties were obtained by using acombination of a fluorochemical repellent and an ionic antistat in athermoset epoxy coating.

Example 51 and Comparative Examples C60-C62

A moisture curable polyurethane resin was prepared by combining oneequivalent of LHT 28 (Union Carbide Corp., Danbury, Conn.), oneequivalent of PPG 3025 (ARCO Chemical Co., Newtown Square, Pa.), and 4equivalents of toluene dissocyanate under a dry nitrogen purge. Themixture was heated with stirring at 80° C. for 4 hours and then cooledto 60° C. A few drops of dibutyltin dilaurate was added to the mixture,and the mixture was allowed to come to room temperature.

A thermoset polyurethane coating was prepared as follows: A portion ofthe resulting moisture curable polyurethane resin (10 grams) was heatedto about 100° C. using a heat gun. About 2 ml of the heated resin waspipetted onto the top of a 25.5 cm by 15.5 cm by 0.102 mm thick primedterephthalate polyester film, and the resin was drawn over the filmusing a No. 12 Meyer bar. The resulting coating was cured at 65° C. for12 hours in a forced air oven and then allowed to stand at ambientconditions for 10 hours. The above procedure was repeated using separate10 gram quantities of urethane resin containing 0.157 gram1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (Antistat10), 0.153 gram Fluorochemical Repellent FR-3, and a combination of0.157 gram 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imideand 0.151 gram Fluorochemical Repellent FR-3, respectively. The curedcoatings were tested for antistatic performance, oil repellency, waterrepellency, and surface resistivity using Test Methods III, IV, V, andVI. The results are shown in Tables 22 and 23.

TABLE 22 Static Charge Dissipation, Oil Repellency, and Water Repellencyof Thermoset Urethane Coatings. Repel- Charge (Kvolts) Decay Rate (sec)Ex. Repellent lency 10% 25% 50% 10% 25% 50% No. (Wt %) Antistat (Wt %) OW RH RH RH RH RH RH C60 None None 1 3 5 5 5 2.4 2.4 2.9 C61 NoneAntistat 10 (1.5%) 1 3 5 5 5 0.01 0.01 0.01 C62 FR-3 (1.5%) None 8 10 55 5 5.4 4.1 2.0 51 FR-3 (1.5%) Antistat 10 (1.5%) 8 10 5 5 5 0.05 0.030.02 RH = relative humidity O = oil W = water

The results in Table 22 show that high oil and water repellency andexcellent antistatic properties were obtained when a combination offluorochemical repellent and ionic antistat were used in a thermoseturethane coating.

TABLE 23 Surface Resistivity of Thermoset Urethane Coatings SurfaceResistivity at 26% RH and Example Repellent Antistat 21.7° C. No. (Wt %)(Wt %) (ohms/square) C60 None None >10E12 C61 None Antistat 10 (1.5%)2.67 × 10E10 C62 FR-3 (1.5%) None >10E12 51 FR-3 (1.5%) Antistat 10(1.5%) 1.75 × 10E10 RH = relative humidity O = oil W = water

The results in Table 23 show that an improvement in antistaticproperties was obtained by using a combination of fluorochemicalrepellent and antistat compound in a thermoset urethane coating.

Various modifications and alterations of this invention will becomeapparent to those skilled in the art without departing from the scopeand spirit of this invention.

1. A process for preparing a water- and oil-repellent, antistaticcomposition comprising the steps of (a) combining (i) at least onenonpolymeric ionic salt consisting of at least one cation and at leastone anion, said cation being selected from the group consisting ofmonovalent metal cations, divalent metal cations, and organic oniumcations, and said anion being a weakly coordinating anion, the conjugateacid of said anion having an acidity greater than or equal to that of ahydrocarbon sulfonic acid, and with the proviso that said anion isorganic or fluoroorganic when said cation is a metal, (ii) at least onefluorochemical repellent, and (iii) at least one thermoplastic polymer;and (b) melt processing a combination of (iii) and at least one of (i)and (ii).
 2. The process of claim 1 wherein either said ionic salt orsaid fluorochemical repellent is combined with said at least onethermoplastic polymer to form said combination, and the other istopically applied to a surface of the melt-processed combination.
 3. Aprocess for preparing a water- and oil-repellent, antistatic compositioncomprising the steps of (a) combining (i) at least one nonpolymericionic salt consisting of at least one cation and at least one anion,said cation comprising an organic onium cation, and said anion being aweakly coordinating anion selected from the group consisting of alkanesulfonates, aryl sulfonates, alkaryl sulfonates, tetraarylborates,carboranes, halogen-substituted carboranes, alkyl-substitutedcarboranes, haloakyl-substituted carboranes, metallocarboranes,teflates, and fluoroorganic anions, the conjugate acid of said anionhaving an acidity greater than or equal to that of a hydrocarbonsulfonic acid, (ii) at least one fluorochemical repellent, and (iii) atleast one thermosetting polymer or ceramer or the reactive precursors ofsaid polymer or ceramer; and (b) allowing the resulting combination tocure.
 4. A process for preparing a water- and oil-repellent, antistaticcomposition comprising the steps of (a) forming a solution by dissolving(i) at least one nonpolymeric ionic salt consisting of at least onecation and at least one anion, said cation comprising an organic oniumcation, and said anion being a weakly coordinating anion selected fromthe group consisting of alkane sulfonates, aryl sulfonates, alkarylsulfonates, tetraarylborates, carboranes, halogen-substitutedcarboranes, alkyl-substituted carboranes, haloakyl-substitutedcarboranes, metallocarboranes, teflates, and fluoroorganic anions, theconjugate acid of said anion having an acidity greater than or equal tothat of a hydrocarbon sulfonic acid, (ii) at least one fluorochemicalrepellent, and (iii) at least one insulating material in (iv) at leastone solvent; (b) casting or coating the solution on to at least onesubstrate; and (c) allowing evaporation of said at least one solvent. 5.A process for preparing a water- and oil-repellent, antistaticcomposition comprising the steps of (a) forming a polymerizablecomposition by combining (i) at least one nonpolymeric ionic saltconsisting of at least one cation and at least one anion, said cationcomprising an organic onium cation, and said anion being a weaklycoordinating anion selected from the group consisting of alkanesulfonates, aryl sulfonates, alkaryl sulfonates, tetraarylborates,carboranes, halogen-substituted carboranes, alkyl-substitutedcarboranes, haloakyl-substituted carboranes, metallocarboranes,teflates, and fluoroorganic anions, the conjugate acid of said anionhaving an acidity greater than or equal to that of a hydrocarbonsulfonic acid, and with the proviso that said anion is organic orfluoroorganic when said cation is a metal, (ii) at least onefluorochemical repellent, and (iii) at least one monomer; and (b)allowing polymerization of the monomer to occur.
 6. The process of claim1 wherein said combining step comprises forming a blend of the ionicsalt, the fluorochemical repellent and the thermoplastic polymer, andsaid melt processing step comprises melt processing the blend.
 7. Theprocess of claim 1 wherein said melt processing step comprises anextrusion step.
 8. The process of claim 1 wherein said melt processingstep comprises a molding step.
 9. The process of claim 1 furthercomprising an annealing step.
 10. The process of claim 1 wherein saidcation comprises an organic onium cation and said at least one weaklycoordinating anion comprises a fluoroorganic anion.
 11. The process ofclaim 1 wherein said at least one weakly coordinating anion is selectedfrom the group consisting of alkane sulfonates, aryl sulfonates, alkarylsulfonates, perfluoroalkanesulfonates, bis(perfluoroalkanesulfonyl)imides, tris(perfluoroalkanesulfonyl)methides,cyanoperfluoroalkanesulfonylamides,bis(cyano)perfluoroalkanesulfonylmethides,bis(perfluoroalkanesulfonyl)methides, andtris(perfluoroalkanesulfonyl)methides.
 12. The process of claim 3wherein said at least one weakly coordinating anion comprises afluoroorganic anion.
 13. The process of claim 3 wherein said at leastone weakly coordinating anion is selected from the group consisting ofalkane sulfonates, aryl sulfonates, alkaryl sulfonates,perfluoroalkanesulfonates, bis(perfluooroalkanesulfonyl)imides,tris(perfluoroalkanesulfonyl)methides,cyanoperfluoroalkanesulfonylamides,bis(cyano)perfluoroalkanesulfonylmethides,bis(perfluoroalkanesulfonyl)methides, andtris(perfluoroalkanesulfonyl)methides.
 14. The process of claim 4wherein said at least one weakly coordinating anion comprises afluoroorganic anion.
 15. The process of claim 4 wherein said at leastone weakly coordinating anion is selected from the group consisting ofalkane sulfonates, aryl sulfonates, alkaryl sulfonates,perfluoroalkanesulfonates, bis(perfluoroalkanesulfonyl)imides,tris(perfluoroalkanesulfonyl)methides,cyanoperfluoroalkanesulfonylamides,bis(cyano)perfluoroalkanesulfonylmethides,bis(perfluoroalkanesulfonyl)methides, andtris(perfluoroalkanesulfonyl)methides.
 16. The process of claim 5wherein said at least one weakly coordinating anion is selected from thegroup consisting of alkane sulfonates, aryl sulfonates, alkarylsulfonates, perfluoroalkanesulfonates,bis(perfluoroalkanesulfonyl)imides,tris(perfluoroalkanesulfonyl)methides,cyanoperfluoroalkanesulfonylamides,bis(cyano)perfluoroalkanesulfonylmethides,bis(perfluoroalkanesulfonyl)methides, andtris(perfluoroalkanesulfonyl)methides.